Systematic synthetic investigations of the quaternary systems Ag - Bi - Q - X (Q = S, Se; X = Cl, Br) led to a variety of quaternary phases that exhibit considerable structural diversity with increasing complexity. These include Ag1.2Bi17.6S23Cl8, AgBi4Se5Br3 and numerous members of the homologous double series Agx(N+1)Bi2+(1-x)(N+1)Q2+(2-2x)(N+1)X2+(2x-1)(N+1) denoted (N, x)P. N represents the order number of a given homologue and x is the degree of substitution of Bi by Ag with 1/2 <= x <= 1. Their structures are built up from two alternating types of modules denoted A and B that are stacked parallel to (001). In module A, rows of edge-sharing [MZ6] octahedra (Z = X and/or Q); M = Ag and/or Bi) running parallel to [010] alternate along [100] with parallel chains of paired monocapped trigonal prisms around Bi atoms. The module type denoted B represents NaCl-type fragments of varying thickness. It is defined by the number N of octahedra within the chain of edge-sharing octahedra running diagonally across it in the (010) plane of the structure. The thickness of module B for current members of the series extends from N = 0 to N = 7. All structures exhibit Ag/Bi disorder in octahedrally coordinated metal positions and Q/X (Q = S, Se; X = Cl, Br) mixed occupation of some anion positions. Some of these compounds are narrow gap semiconductors.

No description available.

No description available.

Featuring size-tunable electrical and optical properties, semiconductor nanocrystals (NCs) attract intensive interest in developing promising functional materials for optoelectronic appli-cations. The surface ligands not only play an important role in the synthesis and colloidal sta-bility of NCs, but also significantly affect their photophysical and electrochemical properties. In this dissertation, I am dealing with the surface ligand engineering of NCs (including both perovskite and metal chalcogenide families) for optical and photocatalytic applications. Polymer ligands are regarded to enable better colloidal stability, durability and processability of fluorescent NCs, which is especially important for perovskite NCs. However, the current wide-used polymer ligands fail to provide sufficient surface passivation for the NCs, which is unfavorable for their luminescence. To address this issue, a dual-ligand system based on par-tially hydrolyzed poly(methyl methacrylate) (h-PMMA) and highly branched polyethyl-enimine (PEI) was designed to stabilize perovskite NCs. The hydrophobic polymer of h-PMMA imparts excellent film-forming properties and durability to the resulting NC-polymer composite. The PEI forms an amino-rich, strongly binding ligand layer on the surface of the NCs being responsible for the significant improvement of the photoluminescence quantum yield and the stability of the resulting material. These superior properties allowed us to fabri-cate a proof-of-concept thin film organic light-emitting diode (OLED) with h-PMMA/PEI-stabilized perovskite NCs. A further insight into the roles of double polymer ligands (h-PMMA and PEI) during the mechanosynthesis of perovskites nanoparticles (NPs) was pro-vided. The h-PMMA can form micelles in the grinding solvent of dichloromethane to act as size-regulating templates for the growth of NPs. The PEI with large amounts of amino groups induced enrichment of PbBr2 in the reaction mixture, which in turn caused the formation of heterostructured CsPbBr3-CsPb2Br5-mPbBr2 and CsPbBr3-Cs4PbBr6-nCsBr NPs. Not only polymer, but also inorganic ligands can be extremely attractive for capping of NCs. In the frame of this thesis, a two-step surface modification strategy was developed to control-lably destabilize the colloidal NCs, which in turn facilitated their 3D assembly into aerogels. Specifically, the long-chain oleic acid ligands were exchanged to the ultra-short-chain inorganic (NH4)2S ligands. These new ligands were further protonated by changing the dispersing solvent, which caused desired colloidal destabilization. The as-prepared CdSe NC aerogels with highly porous and self-supporting structure were found to be attractive for solid-state photocatalysis in a gas phase. Indeed, the (NH4)2S ligand is favourable for the adsorption and activation of substrate molecules (i.e., H2O and CO2) on the large open surface of NC gel, thereby promoting the progress of CO2 photoreduction. As a result, the photocatalytic activity for CO2 reduction of CdSe NC aerogels created in this work is 12-fold higher than that of the pristine non-assembled NC-precipitates.:Abstract 1 Contents 3 Abbreviations 6 List of Figures and Tables 8 1. Colloidal Semiconductor Nanocrystals and their Ligand Shell 13 1.1. Colloidal Semiconductor Nanocrystals 14 1.1.1. Inorganic Core of NCs 15 1.1.1.1. Metal Chalcogenide NCs 16 1.1.1.2. Metal Pnictide NCs 16 1.1.1.3. Halide Perovskites NCs 17 1.1.2. The Surface Ligands for NCs 18 1.1.2.1. The Classification of Surface Ligands based on Head-Groups 18 1.1.2.2. The Classification of Surface Ligands based on Tail-Groups 19 1.2. The Role of Ligands 20 1.2.1. The Role of Ligands in the Synthesis of NCs 20 1.2.2. The Role of Ligand in Colloidal NCs Dispersion and Stability 22 1.2.3. The Role of Ligand in the Light-Matter Interactions as Applied to NCs 24 1.3. The Surface Ligand Engineering of NCs 26 1.3.1. Introducing Ligands during the Synthesis 26 1.3.2. Introducing the Ligands during Post-Synthesis Process 27 1.4. Challenges to be Addressed in this Dissertation 29 2. Polymer Ligands Enhance the Stability and Fluorescence of Perovskite for Optical Application 31 2.1. Background and Motivation 32 2.2. Results and Discussion 34 2.2.1. Spectral Characterization 34 2.2.2. Morphological Characterization 40 2.2.3. Surface Composition 41 2.2.4. Processability, Stability and Durability 43 2.2.5. Green-LED 46 2.3. Conclusions 48 3. Polymer Ligands Assist Mechanosynthesis of Perovskite Nanoparticles 49 3.1. Background and Motivation 50 3.2. Results and Discussion 50 3.2.1 Morphology and Composition 51 3.2.2 Formation and Phase Conversion of the Nanoparticles 53 3.2.3. Spectral Characterization 58 3.3. Conclusions 60 4. Ligand Protonation Promote 3D Assembly of CdSe Nanocrystals for CO2 Photoreduction 62 4.1. Background and Motivation 63 4.2. Results and Discussion 64 4.2.1. The Gelation Method 64 4.2.2. Surface Composition of the NC Aerogels 67 4.2.3. Performance of CdSe-S Aerogels in Photoreduction of CO2 68 4.2.4. Photocatalytic Mechanism of the CdSe-S/Ni Aerogel 70 4.3. Conclusion 73 5. Conclusions and Perspectives 75 Appendix. Experimental Section 78 A.1. Reagents 78 A.2. NCs synthesis 78 A.2.1 Mechanosynthesis of Polymer-Coordinated Perovskite NCs 78 A.2.2 Oil Phase Synthesis of Colloidal CdSe NCs 79 A.2.3 Ligand Protonation-Promoted Assembly of CdSe-S NCs into Gel 79 A.3. Optical and Photocatalytic Applications of NCs 80 A.3.1 Optical Applications of Polymer-Stabilized Perovskite NCs 80 A.3.2 Photocatalytic Applications of CdSe-S Aerogels 80 A.4. Characterization Methods 81 A.4.1 Morphology Characterization 81 A.4.2.Element Characterization 81 A.4.3 Diffraction Characterization 82 A.4.4 Spectroscopy Characterization 82 A.4.5 Gas adsorption Measurement 82 A.4.6 Electrochemical Measurements 83 A.4.7 Other Characterizations 83 A.5. Additional Data 84 Bibliography 87 List of Publications 96 Acknowledgements 98 Erklärung 100

<p dir="ltr">For reliable, facile, and user-friendly, solution-based synthesis of materials, the colloidal nanocrystal route has proven to be the method of choice for so many. The tunability that this process renders its users---from choice of precursors, solvent systems, and reaction conditions including temperature, pressure, and precursor addition order---is truly second to none. In their simplest form, these nanomaterials are usually comprised of an inorganic core of the desired material and an outer layer of surface-stabilizing molecules called ligands. These ligands provide colloidal stability and allow for the solution-processing of these materials for downstream usage in devices such as light-emitting diodes and photovoltaics, for example. In this thesis, the study and use of colloidal nanomaterials of Cu(In,Ga)(S,Se)₂ (CIGSSe), IIA-IVB-S₃ (including BaZrS₃ and SrZrS₃), alkaline earth polysulfides (IIAS_x; IIA = Sr, Ba; x = 2, 3), and other materials like Cu₂GeS₃ and Cu₂BaSnS₄, for studies into the formation, colloidal stability, and fabrication into solar cells was performed.</p><p dir="ltr">More specifically, an experimental protocol was developed to fabricate high-quality CIGSSe nanoparticles with carbonaceous residues that are substantially reduced from traditional pathways. Traditional methods for synthesizing colloidal CIGS NPs often utilize heavy, long-chain organic species to serve as surface ligands which, during annealing in a Se/Ar atmosphere, leave behind an undesirable carbonaceous residue in the film. In an effort to minimize these residues, N-methyl-2-pyrrolidone (NMP) was used as an alternative surface ligand. Through the use of the NMP-based synthesis, a substantial reduction in the number of carbonaceous residues was observed in selenized films. Additionally, the fine-grain layer at the bottom of the film, a common observation of solution-processed films from organic media, was observed to exhibit a larger average grain size and increased chalcopyrite character over those of traditionally prepared films, presumably as a result of the reduced carbon content, allowing for superior growth. As a result, a gallium-free CuIn(S,Se)₂ device was shown to achieve power-conversion efficiencies of over 11% as well as possessing exceptional carrier generation capabilities with a short-circuit current density (J_SC) of 41.6 mA/cm², which is among the highest for the CIGSSe family of devices fabricated from solution-processed methods. It was shown that pre-selenized films of sulfide nanoparticles instead of selenide nanoparticles performed better as solar cells. While the exact mechanism is still under debate, it appears that the growth phase during selenization, which varies depending on the chalcogen present in the starting material plays an important role.</p><p dir="ltr">The IIA-IVB-S₃ system is just beginning to emerge as a material system shown to be capable of solution-based synthesis methods. This is primarily due to the extremely high oxophilicity of the IVB elements, Ti, Zr, and Hf, necessitating that extreme care and judicial use of inert environments be used to synthesize these materials via solution-based methods. In the IIA-IVB-S₃ system exists some of the chalcogenide perovskites, including BaZrS₃, which are expected to have similar electronic properties to the well-known, high-performing halide perovskites, albeit much more stable, making them attractive prospects as novel semiconductor materials for optoelectronic applications. This work builds upon recent studies to show a general synthesis protocol, involving the use of carbon disulfide insertion chemistry to generate highly reactive precursors, that can be used towards the colloidal synthesis of numerous nanomaterials in the IIA-IVB-S₃ system, including BaTiS₃, BaZrS₃, BaHfS₃, α-SrZrS₃ and α-SrHfS₃. Additionally, we establish a method to reliably control the formation of the BaZrS₃ perovskite, a complication seen in previous literature where BaZrS₃ appears to exist as two different phases when synthesized via colloidal methods. The utility of these nanomaterials is also assessed via the measurement of their absorption properties and in the form of highly stable colloidal inks for the fabrication of homogenous, crack-free thin films of BaZrS₃. In addition to the chalcogenide perovskites, the IIA-S system was also explored to better understand the solution-based formation of these materials and how the control of IIA polysulfides can be achieved. We show that the synthesis of these materials is strongly correlated to the reaction temperature and that the length of the S_n^2- oligomer chain is the dependent variable. We also report on the synthesis of a previously unreported polymorph of SrS₂ which appears to take on the <i>C2/c</i> space group, the same as BaS₂.</p><p dir="ltr">Finally, some discussion is also provided on the use of transmission electron microscopy (TEM) to analyze the crystal structure of materials. Some tips and techniques used throughout this thesis are summarized in this section.</p>

In this thesis work, a systematic quantitative study has been undertaken, on the performance of etched fiber Bragg Grating (FBG) sensors in the investigation of surface molecular adsorption in real-time; it is shown that the limit of detection (LOD) of FBGs etched below 2 microns diameter, is better compared to prominent optical label-free molecular sensing techniques such as Surface Plasmon Resonance (SPR). Novel fiber optic sensors based on FBG and etched FBG with various nano materials (polyelectrolytes, carbon nanotubes, hydrogel, metals and chalcogenides) coated on the surface of the core or cladding, have been proposed for sensing multi parameters such as pH, protein, humidity, gas, strain, temperature, and light etc. Besides being reproducible and repeatable, the proposed methods are fast, compact, and highly sensitive. A novel optical instrument has also been developed to measure angular deviation, binocular deviation and refractive index of glass slabs, and liquids, based on a shadow casting technique. This method uses the deviation in the geometrical shadow cast by a periodic dot pattern trans-illuminated by a distorted light beam from the transparent test specimen relative to a reference pattern.

Chalcogenide glasses (ChGs) are produced by alloying together a “chalcogen” element” (S, Se or Te) with other elements, generally from group V (Sb, As) or group IV (Ge, Si) to form covalently bonded solids. A variety of stable non-crystalline materials can be prepared in bulk, fiber, and thin film forms using melt-quenching, vacuum deposition, and other less common techniques. Being amorphous semiconductors, ChGs exhibit a variety of photo-induced phenomena when irradiated with proper light and therefore find a wide range of technological applications (optical data storage, telecommunications, IR optics, etc). As research in this field is strongly driven by the needs of high-tech industry, physical properties related to the applications are more systematically investigated than the atomic structure, which is ultimately related to the macroscopic properties. A shortcoming of not having yet established microstructure-properties relations in ChGs is the lack of a strategic design of new materials for specific applications. The present study is a systematic investigation of properties for various families of ChGs using experimental techniques that probe structure (near infrared Raman scattering, x-ray and neutron diffraction, EXAFS), dynamics (IR-Photon correlation spectroscopy), thermal properties (differential scanning calorimetry) and glass morphology (scanning electron microscopy). Particular emphasis is given on binary and pseudo-ternary ChGs, which are the basis of more complex multi-component glasses, such as As-Se, Sb-Se, As-Te, Ge-S, Ge-S-AgI, As-Se-AgI, As-Se-Ag, As-S-AgI, As-S-Ag etc. over a wide glass composition range. The binary systems are known for their significant optical properties while the Ag-doped glasses belong to the class of superionic conductors. Although some of these glass-forming systems have been extensively studied in the literature, several details concerning the atomic arrangement are still not fully understood, partly due to that some of these glasses are phase separated at the microscale; a fact that is usually overlooked in related studies. In the present study, using high-resolution off-resonant Raman conditions and a more elaborate analysis of the Raman spectra, in conjunction with thermal and morphological data, we have been able to obtain a better understanding of atomic structure and to advance structure-properties relations for both the homogeneous and phase separated glasses. / Μια κατηγορία υαλωδών υλικών, γνωστή ως χαλκογονούχες ύαλοι αρχίζει να κερδίζει σημαντικό έδαφος στον τομέα των εφαρμογών λόγω των φωτονικών ιδιοτήτων που διαθέτουν. Ως χαλκογονούχες ύαλοι θεωρούνται οι υαλώδεις ενώσεις στις οποίες ένα τουλάχιστον περιέχει ένα από τα στοιχεία χαλκογόνων S, Se, και Te. Η ανάμιξη των στοιχείων αυτών με στοιχεία όπως Sb, As, Ge, Si, κλ.π. οδηγεί στο σχηματισμό σταθερών ομοιοπολικών υαλωδών ενώσεων. Το γεγονός ότι οι χαλκογονούχες ύαλοι είναι άμορφοι ημιαγωγοί έχει ως αποτέλεσμα την εμφάνιση πλήθους φωτο-επαγόμενων φαινομένων όταν οι ενώσεις αυτές ακτινοβοληθούν με φως κατάλληλου μήκους κύματος (συγκρίσιμο με το ενεργειακό τους χάσμα). Οι φωτο-επαγόμενες αλλαγές απορρέουν από τις αλλαγές οι οποίες επέρχονται στην ατομική δομή του υλικού (φωτο-δομικές αλλαγές). Τα φωτο-επαγόμενα φαινόμενα είναι εκμεταλλεύσιμα σε πλήθος τεχνολογικών εφαρμογών, για παράδειγμα στην οπτική αποθήκευση πληροφορίας (DVD), σε οπτικά που λειτουργούν στο υπέρυθρο, στις τηλεπικοινωνίες κλπ. Καθώς η έρευνα πάνω στο εν λόγω επιστημονικό πεδίο καθορίζεται σε μεγάλο βαθμό από τις ανάγκες για βιώσιμες τεχνολογικές εφαρμογές, οι φυσικές ιδιότητες, οι οποίες σχετίζονται άμεσα με τις εφαρμογές, έχουν μελετηθεί εντατικότερα και πιο συστηματικά από την ατομική δομή η οποία είναι κατά βάση υπεύθυνη για τα φωτο-επαγόμενα φαινόμενα. Αυτό έχει ως μειονέκτημα την απουσία συσχετισμών μεταξύ μικροσκοπικών και μακροσκοπικών ιδιοτήτων με αποτέλεσμα την απουσία στρατηγικού σχεδιασμού νέων λειτουργικών υλικών με τις επιθυμητές ιδιότητες. Η παρούσα διατριβή περιλαμβάνει μια συστηματική μελέτη διαφόρων οικογενειών χαλκογονούχων υάλων με τη χρήση πειραματικών τεχνικών οι οποίες διερευνούν την ατομική δομή (σκέδαση Raman, περίθλαση ακτίνων-X και νετρονίων, EXAFS), τις θερμικές ιδιότητες (διαφορική θερμιδομετρία σάρωσης) και την μορφολογία των υάλων (ηλεκτρονική μικροσκοπία σάρωσης). Ιδιαίτερη έμφαση δόθηκε σε δυαδικά και ψευδο-δυαδικά συστήματα χαλκογονούχων υάλων τα οποία συμπεριλαμβάνουν As-Se, Sb-Se, As-Te, Ge-S, Ge-S-AgI, As-Se-AgI, As-Se-Ag, As-S-AgI, As-S-Ag κλπ. για μεγάλο εύρος συστάσεων της κάθε οικογένειας. Τα δυαδικά συστήματα είναι γνωστά για τις εξαίρετες οπτικές τους ιδιότητες ενώ οι ύαλοι με προσμίξεις Αργύρου ανήκουν στην κατηγορία των υπεριοντικών υάλων με αρκετά υψηλές ιοντικές αγωγιμότητες που χαρακτηρίζονται από μικροσκοπικό διαχωρισμό φάσεων σε συγκεκριμένες συγκεντρώσεις του Αργύρου. Παρά το γεγονός ότι ορισμένα από τα προαναφερθέντα άμορφα υλικά έχουν κατ’ επανάληψη μελετηθεί στο παρελθόν, ακριβείς πληροφορίες σχετικά με την ατομική δομή τους δεν είναι διαθέσιμες, εν μέρει εξ’ αιτίας της ελλιπούς πειραματικής προσέγγισης και εν μέρει λόγω του μικροσκοπικού διαχωρισμού φάσεων που χαρακτηρίζει τις υάλους με πρόσμιξη Αργύρου, γεγονός το οποίο συχνά αμελείται σε προγενέστερες μελέτες. Στην παρούσα διατριβή, χρησιμοποιώντας τη φασματοσκοπία σκέδασης Raman υψηλής ανάλυσης και μακριά από συνθήκες συντονισμού, σε συνδυασμό με θερμικά και μορφολογικά δεδομένα των υάλων, κατέστη δυνατό να αποκτηθεί μια πιο σφαιρική γνώσης σχετικά με την ατομικής κλίμακας δομή των υάλων και να προαχθούν συσχετισμοί δομής-ιδιοτήτων τόσο για ομοιογενή όσο και για ανομοιογενείς υάλους.

Le mélange à quatre ondes est un effet non linéaire sensible à la phase qui suscite de nombreux intérêts dans le domaine de la génération de peignes de fréquences et du traitement tout optique du signal par exemple. Un peigne de fréquences peut en effet s'obtenir par effet de mélange à quatre ondes 1en cascade. Dans ce cas, un nombre N d'ondes interagissent entre elles via l'effet Kerr et la modélisation d'un tel processus doit tenir compte de tous les couplages possibles entre les ondes. Au cours de mes travaux de thèse, je me suis intéressé, dans un premier temps, à la modélisation du mélange à quatre ondes dit multiple pour lequel un nombre quelconque N d'ondes interagissent entre elles. J'ai proposé une formulation générale permettant d'identifier simplement tous les termes de mélange à quatre ondes issus de toutes les combinaisons possibles de couplage entre les ondes et leur désaccord de phase associé. J'ai validé cette approche en proposant une étude théorique et expérimentale d'un processus de mélange à quatre ondes multiple dans une fibre optique non linéaire. Dans une deuxième partie, j'ai proposé, grâce au modèle élaboré précédemment, une étude théorique du phénomène de conversion de fréquence sensible à la phase, permettant la décomposition des composantes en quadrature d'un signal optique. Dans la littérature, cette expérience fut démontrée initialement avec quatre ondes pompes et dans plusieurs types de composants non linéaires. J'ai pu démontrer, au cours de mes travaux, que trois pompes étaient suffisantes pour réaliser l'expérience et j'ai déterminé des relations analytiques simples permettant de choisir les paramètres expérimentaux (notamment l'amplitude et la phase des pompes) rendant possible la décomposition des composantes en quadrature d'un signal. J'ai validé cette étude par la démonstration expérimentale d'un convertisseur de fréquence sensible à la phase avec uniquement trois pompes et j'ai étudié théoriquement les effets de la dispersion chromatique sur les performances du convertisseur de fréquence. Enfin, dans une dernière partie, j'ai caractérisé des fibres optiques microstructurées en verre de chalcogénure fabriquées dans le cadre d'une collaboration avec Perfos, l'Institut des Sciences Chimiques de Rennes et SelenOptics. Dans ce cadre, j'ai mis en place un banc de mesure de la dispersion chromatique et du coefficient non linéaire des fibres optiques basé sur le mélange à quatre ondes. / Four-wave mixing is a phase-sensitive nonlinear effect that arouses interest, particularly in the fields of frequency comb generation and all-optical signal processing. As an example, frequency combs can be produced thanks to a cascaded four-wave mixing process. In this case, N waves can interact with each other through the optical Kerr effect, and one has to take into account all the possible interactions to be able to adequately model the process. During my PhD thesis, I was interested in modeling the so-called multiple four-wave mixing process, in which any number N of waves can interact with each other. I proposed a general formulation that allows to easily identify all the four-wave mixing terms originating from all the possible combinations of wave coupling and their associated phase-mismatch terms. I validated this approach through the theoretical and experimental study of a multiple four-wave mixing process in a nonlinear optical fiber. Thanks to the developed model, I then proposed a theoretical study of the phase-sensitive frequency conversion process, which permits to demultiplex the quadrature components of an optical signal. In the literature, this process was first experimentally demonstrated in several nonlinear devices using four pump waves. I demonstrated that only three pump waves were required to successfully perform the experiment, and I determined the simple analytical relations from which the adequate experimental parameters (namely, the amplitudes and phases of the pump waves) could be deduced. I finally validated this study by experimentally demonstrating a phase-sensitive frequency conversion process with only three pump waves, and I theoretically studied the influence of chromatic dispersion on the performance of this frequency converter. Finally, I characterized some chalcogenide microstructured optical fibers that were fabricated in the framework of a collaboration with Perfos, the Institut des Sciences Chimiques de Rennes, and SelenOptics. I set up a test bench based on the four-wave mixing process in order to measure the chromatic dispersion and nonlinear coefficient of some optical fibers.

Le marché du stockage de l'énergie est en perpétuelle expansion, tant pour les applications nomades que fixes. Afin de répondre aux exigences requises pour les diverses applications (appareils électroniques, véhicules hybrides et électriques, stockage des énergies renouvelables…), des batteries toujours plus performantes, compactes et légères doivent être développées. Pour cela, les batteries utilisant du lithium métallique en tant qu'anode sont les plus attractives en termes de densités d'énergies. Néanmoins, l'utilisation d'électrolytes liquides conventionnels, généralement des solvants organiques inflammables, dans de tels dispositifs soulève des problématiques de sécurité. Les travaux de recherche présentés dans ce manuscrit concernent l'étude de matériaux vitreux pouvant être utilisés en tant qu'électrolyte solide afin de permettre le développement de batteries tout-solide sûres et performantes. Des verres de sulfures au lithium, attractifs pour leurs propriétés de conduction ionique, sont étudiés et caractérisés. Les propriétés de conduction ionique dans les verres étant toujours mal comprises et sujettes à controverses, l'analyse structurale des verres présente ici un réel intérêt pour une meilleure compréhension des corrélations entre structure et propriétés. Un effort de recherche a donc été porté sur l'étude de l'ordre local dans les verres préparés via différentes techniques d'analyse structurale complémentaires. Enfin, les matériaux vitreux, sont de manière générale relativement faciles à mettre en forme. Les verres étudiés dans ce manuscrit peuvent alors également être utilisés en tant qu'électrolytes sous forme de couches minces dans les micro-batteries. Des premiers essais de dépôts par pulvérisation cathodique RF magnétron de couches minces conductrices ont donc été effectués et constituent la première brique à la fabrication de micro-batteries. / The energy storage market is in constant growth for both portable and stationary applications. To satisfy the requirements of various applications (electronic devices, hybrid-electric vehicles, renewable energy storage…), always more efficient, more compact and lightweight batteries have to be developed. Then, thanks to their high energy densities, batteries using Li metal anodes are the most promising to complete this challenge. However, the use of conventional liquid electrolytes raises safety issues, mainly related to the flammability of the organic liquid. In this thesis, glassy materials, exhibiting great interest towards developing solid electrolytes are considered and might enable the development of safe and efficient all-solid-state batteries. Here, Li-sulfide glasses, attractive for their ionic conduction properties, have been studied and characterized. The ionic conduction properties of glasses are still misunderstood and controversial, the structural investigation of glasses is of great interest in order to get a better understanding of structure-properties relationship. Then, the short and intermediate range order of prepared glasses have been investigated by the mean of various complementary structural analysis techniques. Finally, glassy materials are usually quite easy to shape. Thus, studied glasses in this thesis can also be used as thin-film electrolytes in microbatteries. First tests of sputtering of conducting thin-films have been performed by RF magnetron sputtering and constitute a first step in order to design microbatteries.

Im Rahmen der vorliegenden Arbeit wurden Metallchalkogenid-Nanopartikel bzw. Quantum Dots größenselektiv mittels kontinuierlicher MicroJet-Reaktor-Technologie in wässrigem Medium erzeugt. Aufgrund der sehr kurzen Mischzeiten im µs- bis ms-Bereich können Keimbildung und -wachstum im MicroJet-Reaktor zeitlich voneinander separiert werden. Die Begrenzung des Partikelwachstum durch den Einsatz von Stabilisatoren oder geringer Präkursorkonzentrationen ermöglichten die Synthese von monodispersen, nanokristallinen Produkten mit sehr schmaler Partikelgrößenverteilung. Ausgehend von den wasserlöslichen Präkursoren Cadmiumnitrat und Natriumsulfid wurde sowohl eine Synthesestrategie für elektrostatisch- als auch Liganden-stabilisierte CdS-Nanopartikel entwickelt. Es wurden zahlreiche Reaktionsparameter wie Temperatur, Präkursorverhältnis, Konzentration oder Fällungsmittel variiert und der Einfluss auf die Partikelgröße überprüft. In weiteren Untersuchungen konnte die Übertragbarkeit der MicroJet-Reaktor-Synthese auf die Metallchalkogenide Cadmiumzinksulfid, Silbersulfid und Silberindiumsulfid validiert werden. Auch komplexere Systeme wie Core/Shell Partikel sind mittels postsynthetischer Beschichtung der im MicroJet-Reaktor hergestellten Nanopartikel möglich. Erste Experimente zur Synthese von CdSe bestätigten die Eignung des kontinuierlichen Verfahrens zur Fällung höherer Chalkogenide.:1 Einleitung 1 1.1 Halbleiternanopartikel 3 1.1.1 Bandstruktur des Festkörpers 3 1.1.2 Interbandübergänge in direkten und indirekten Halbleitern 7 1.1.3 Quantum Confinement 15 1.2 Fällung von Nanopartikeln im MicroJet-Reaktor 20 1.2.1 Partikelbildung durch Kristallisation 20 1.2.2 Funktionsprinzip des MicroJet-Reaktors 22 1.2.3 State of the Art 25 1.3 Nanoskalige Metallchalkogenide 29 1.3.1 Cadmiumchalkogenide 29 1.3.2 Near-Infrared Quantum Dots 31 1.3.3 Core/Shell-Partikel 34 1.4 Zielsetzung 37 2 Ergebnisse und Diskussion 39 2.1 Allgemeines 39 2.2 Cadmiumchalkogenide 47 2.2.1 Hydrothermalsynthese von CdS im Laborautoklaven 47 2.2.1.1 Wiederholbarkeit 48 2.2.1.2 Einfluss des Präkursorverhältnis 50 2.2.1.3 Versuchsplanung zur Untersuchung ausgewählter Reaktionsparameter 51 2.2.1.4 Effektberechnung zur Untersuchung ausgewählter Einflussfaktoren 54 2.2.1.5 Beobachtungen und Charakterisierung 56 2.2.2 Kontinuierliche Synthese von CdS im MicroJet-Reaktor 62 2.2.2.1 MJR-Synthese von CdS aus Cd(NO3)2 und Na2S 62 2.2.2.2 MJR-Synthese von CdS aus Cd(NO3)2 und Thioacetamid 71 2.2.3 CdS/ZnS Core/Shell und Cd1-xZnxS Quantum Dots 76 2.2.3.1 CdS/ZnS Core/Shell Quantum Dots 77 2.2.3.2 Cd1-xZnxS Quantum Dots 88 2.2.4 Hydrothermalsynthese von CdSe im Laborautoklaven 99 2.2.4.1 Wiederholbarkeit 99 2.2.4.2 Präkursorverhältnis Cd2+:Se2- 101 2.2.4.3 Versuchsplanung zur Untersuchung ausgewählter Reaktionsparameter 104 2.2.4.4 Effektberechnung zur Untersuchung ausgewählter Einflussfaktoren 108 2.2.4.5 Beobachtungen und Charakterisierung 111 2.2.5 Kontinuierliche Synthese von CdSe im MicroJet-Reaktor 116 2.3 Near-Infrared Quantum Dots 121 2.3.1 Kontinuierliche Synthese von AgS2 im MJR-Reaktor 121 2.3.1.1 Elektrostatisch stabilisierte Ag2S Quantum Dots 121 2.3.1.2 Ag2S/ZnS Core/Shell Quantum Dots 138 2.3.1.3 Ligandenstabilisierte Ag2S Quantum Dots 143 2.3.2 Kontinuierliche Synthese von Indiumsilbersulfid im MJR-Reaktor 152 3 Experimenteller Teil 165 3.1 Synthesen 165 3.1.1 Verwendete Chemikalien 165 3.1.2 Hydrothermalsynthese im Laborautoklaven 166 3.1.2.1 Versuchsaufbau 166 3.1.2.2 Cadmiumsulfid 167 3.1.2.3 Cadmiumselenid 168 3.1.2.4 Silbersulfid 169 3.1.3 Kontinuierliche Synthese im MicroJet-Reaktor 169 3.1.3.1 Versuchsaufbau und Durchführung der MicroJet-Reaktor-Synthese 169 3.1.3.2 Synthese Liganden-stabilisierter Metallsulfide 171 3.1.3.3 Synthese elektrostatisch stabilisierter Metallsulfide 171 3.1.3.4 Synthese von Cadmiumselenid 172 3.1.3.5 Synthese von Core-Shell-Partikeln 172 3.2 Analytische Methoden 173 3.2.1 Dynamische Lichtstreuung (DLS) 173 3.2.2 Statische Lichtstreuung (SLS) 173 3.2.3 UV/Vis-Absorptionsspektroskopie 173 3.2.4 Photolumineszenz (PL)-Spektroskopie 174 3.2.5 Transmissionselektronenmikroskopie (TEM) 174 3.2.6 Rasterelektronenmikroskopie (REM) 175 3.2.7 Optische Emissionsspektroskopie mit induktiv gekoppeltem Plasma (ICP-OES) 175 3.2.8 Röntgenfluoreszenzanalyse (RFA) 176 3.2.9 Pulver-Röntgendiffraktometrie (PXRD) 176 3.2.10 RAMAN-Spektroskopie 177 3.2.11 Abgeschwächte Totalreflexions-Infrarotspektroskopie (ATR-FTIR) 177 4 Zusammenfassung und Ausblick 179 5 Literatur 182 6 Anhang 195 / In the present work, metal chalcogenide nanoparticles or Quantum Dots were obtained size-selectively using continuous MicroJet Reactor technology. Due to the short mixing times in the µs to ms range, crystallite nucleation and crystal growth are well separated and enable concentration-limited particle growth. Alternatively, particle growth can be limited by stabilizers. Starting from the water-soluble precursors Cd(NO3)2 and Na2S, a synthesis strategy for both electrostatic and ligand stabilized CdS nanoparticles in aqueous medium was developed. The nanocrystalline products obtained were characterized by a narrow, monodisperse particle size distribution. Examining the influence of the particle size, numerous reaction parameters e. g. temperature, ratio of precursors, concentration or precipitant were varied. In further investigations, the transferability of the MicroJet Reactor synthesis to the metal chalcogenides (Cd,Zn)S, Ag2S and AgInS2 was validated. By means of post-synthetic coating of the nanoparticles produced in the MicroJet Reactor, more complex systems such as CdS/ZnS or Ag2S/ZnS core/shell particles are accessible. Initial experiments on the synthesis of CdSe confirmed the suitability of the continuous process for precipitation of selenides.:1 Einleitung 1 1.1 Halbleiternanopartikel 3 1.1.1 Bandstruktur des Festkörpers 3 1.1.2 Interbandübergänge in direkten und indirekten Halbleitern 7 1.1.3 Quantum Confinement 15 1.2 Fällung von Nanopartikeln im MicroJet-Reaktor 20 1.2.1 Partikelbildung durch Kristallisation 20 1.2.2 Funktionsprinzip des MicroJet-Reaktors 22 1.2.3 State of the Art 25 1.3 Nanoskalige Metallchalkogenide 29 1.3.1 Cadmiumchalkogenide 29 1.3.2 Near-Infrared Quantum Dots 31 1.3.3 Core/Shell-Partikel 34 1.4 Zielsetzung 37 2 Ergebnisse und Diskussion 39 2.1 Allgemeines 39 2.2 Cadmiumchalkogenide 47 2.2.1 Hydrothermalsynthese von CdS im Laborautoklaven 47 2.2.1.1 Wiederholbarkeit 48 2.2.1.2 Einfluss des Präkursorverhältnis 50 2.2.1.3 Versuchsplanung zur Untersuchung ausgewählter Reaktionsparameter 51 2.2.1.4 Effektberechnung zur Untersuchung ausgewählter Einflussfaktoren 54 2.2.1.5 Beobachtungen und Charakterisierung 56 2.2.2 Kontinuierliche Synthese von CdS im MicroJet-Reaktor 62 2.2.2.1 MJR-Synthese von CdS aus Cd(NO3)2 und Na2S 62 2.2.2.2 MJR-Synthese von CdS aus Cd(NO3)2 und Thioacetamid 71 2.2.3 CdS/ZnS Core/Shell und Cd1-xZnxS Quantum Dots 76 2.2.3.1 CdS/ZnS Core/Shell Quantum Dots 77 2.2.3.2 Cd1-xZnxS Quantum Dots 88 2.2.4 Hydrothermalsynthese von CdSe im Laborautoklaven 99 2.2.4.1 Wiederholbarkeit 99 2.2.4.2 Präkursorverhältnis Cd2+:Se2- 101 2.2.4.3 Versuchsplanung zur Untersuchung ausgewählter Reaktionsparameter 104 2.2.4.4 Effektberechnung zur Untersuchung ausgewählter Einflussfaktoren 108 2.2.4.5 Beobachtungen und Charakterisierung 111 2.2.5 Kontinuierliche Synthese von CdSe im MicroJet-Reaktor 116 2.3 Near-Infrared Quantum Dots 121 2.3.1 Kontinuierliche Synthese von AgS2 im MJR-Reaktor 121 2.3.1.1 Elektrostatisch stabilisierte Ag2S Quantum Dots 121 2.3.1.2 Ag2S/ZnS Core/Shell Quantum Dots 138 2.3.1.3 Ligandenstabilisierte Ag2S Quantum Dots 143 2.3.2 Kontinuierliche Synthese von Indiumsilbersulfid im MJR-Reaktor 152 3 Experimenteller Teil 165 3.1 Synthesen 165 3.1.1 Verwendete Chemikalien 165 3.1.2 Hydrothermalsynthese im Laborautoklaven 166 3.1.2.1 Versuchsaufbau 166 3.1.2.2 Cadmiumsulfid 167 3.1.2.3 Cadmiumselenid 168 3.1.2.4 Silbersulfid 169 3.1.3 Kontinuierliche Synthese im MicroJet-Reaktor 169 3.1.3.1 Versuchsaufbau und Durchführung der MicroJet-Reaktor-Synthese 169 3.1.3.2 Synthese Liganden-stabilisierter Metallsulfide 171 3.1.3.3 Synthese elektrostatisch stabilisierter Metallsulfide 171 3.1.3.4 Synthese von Cadmiumselenid 172 3.1.3.5 Synthese von Core-Shell-Partikeln 172 3.2 Analytische Methoden 173 3.2.1 Dynamische Lichtstreuung (DLS) 173 3.2.2 Statische Lichtstreuung (SLS) 173 3.2.3 UV/Vis-Absorptionsspektroskopie 173 3.2.4 Photolumineszenz (PL)-Spektroskopie 174 3.2.5 Transmissionselektronenmikroskopie (TEM) 174 3.2.6 Rasterelektronenmikroskopie (REM) 175 3.2.7 Optische Emissionsspektroskopie mit induktiv gekoppeltem Plasma (ICP-OES) 175 3.2.8 Röntgenfluoreszenzanalyse (RFA) 176 3.2.9 Pulver-Röntgendiffraktometrie (PXRD) 176 3.2.10 RAMAN-Spektroskopie 177 3.2.11 Abgeschwächte Totalreflexions-Infrarotspektroskopie (ATR-FTIR) 177 4 Zusammenfassung und Ausblick 179 5 Literatur 182 6 Anhang 195