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No description available.

Electronic Packaging is currently deeply in need of new solutions concerning vertical interconnection strategies. With respect to downscaling the geometrical limits, entering the nanoscale for first-level interconnects is nothing more than a consequence. This thesis proposes a new strategy for highly resolved vertical interconnects that are realized by metallic nanowires (NWs). These are embedded inside a dielectric matrix enabling the further raster size reduction for chip interconnects. The creation of NW arrays in self-ordering templates (anodized Al2O3 (AAO) and track-etched poly carbonate) by electrochemical deposition of Ag and Ni inside the pores of these as well as the characterisation of the NWs' properties with respect to the film's applicability are to the fore. Electrical properties are shown to be sensitive to the mode of deposition. Crystallographic properties do not seem to be responsible for this while the NWs' morphology slightly differs and is therefore expected to remarkably influence electron transport. Additionally, the deposition mechanism in high-aspect-ratio pores of AAO is in another focus of investigation. This process was in the past described as diffusively controlled, but this assertion was not further evaluated. The presence of a gradient in the diffusion coefficient as well as the presence and expansion of an electrochemical double layer located at the template's inner surface are responsible limiting the deposition process. An existing model of porous electrodes is compared to the measured data and found not to be valid for the system of highly recessed ultramicroelectrode arrays by which this system is described. Therefore a new model that differentiates between charge-transfer and diffusive motion is proposed and shown to fit to the system's properties. Apart from mechanistic investigations, the implementation of the obtained NW arrays as an interconnector film proposes these to be applied best by adhesive bonding. Bonding properties were found to be well realizable by the additional coverage of the filled membranes with a polymer thin film. This can easily be attached onto the film by spin-coating the corresponding monomer and reactive curing while already being embedded in the package. Alternative methods for contact formation, such as non-reactive bonding and nanosoldering using segmented NWs, are proposed. The strategy is shown to still lack important technological questions while the findings with respect to fabrication, growth and implementation are very promising. / Die Aufbau- und Verbindungstechnik der Elektronik wird in absehbarer Zeit Größenskalen erreichen, bei denen die verwendeten Materialien in der ersten Kontaktierungsebene als Nanomaterialien zu bezeichnen sind, das heißt ≤ 100 nm sind. Des Weiteren bestehen momentan nur bedingt viele Ansätze zu deren Implementierung in Vertikalverbindungsstrukturen (zum Beispiel für die dreidimensionale Integration). Die vorliegende Dissertation schlägt daher vor, die vertikale Verbindung über einen zwischen die Chips laminierbaren Film mit hochdichten und vertikal ausgerichteten nanoskaligen Drähten (NWs) zu realisieren. Diese sind in einer dielektrischen Matrix fixiert und gewährleisten die elektrische Anisotropie des Kontaktfilms. Innerhalb dieser Matrix werden die metallischen Drähte durch elektrochemische Abscheidung erzeugt. Der Fokus dieser Arbeit liegt somit auf der Charakterisierung des reduktiven Wachstumsprozesses von Ag und Ni innerhalb dünner Poren. Dabei können die Eigenschaften durch verschiedene Abscheidemodi gezielt beeinflusst werden. Hinsichtlich der elektrischen Eigenschaften ergibt sich im Vergleich zu der zugrundeliegenden Kristallographie ein wesentlich stärkerer Einfluss der Draht-Morphologie. Der Prozess der Porenfüllung wird im Allgemeinen als stark diffusionskontrolliert angenommen, wurde jedoch bisher nicht weiter quantifiziert. Die der Abscheidung zugrundeliegenden Prozesse Elektrolytdiffusion, Ladungstransfer an der Elektrode und Migrationsbeeinflussung durch die Porengeometrie werden daher voneinander getrennt und einzeln charakterisiert. Das vorliegende System kann als Matrix von stark versenkten Ultramikroelektroden abstrahiert werden. Existente Modelle zur Beschreibung derartiger Systeme treffen auf den vorliegenden Fall im Allgemeinen nicht zu, sodass basierend auf elektrochemischen Untersuchungen ein variiertes Abscheidemodell vorgeschlagen wird. Dieses berücksichtigt die Nicht-Linearität der elektrochemischen Doppelschicht, die von der Porenoberfläche ausgeht sowie deren Frequenzabhängigkeit. Neben mechanistischen Untersuchungen schließen sich Versuche an, deren Fokus auf der direkten Anwendung der mit Nanodrähten gefüllten Membranen liegt. Dabei wird vornehmlich deren Fixierung per Klebeverbindung angestrebt. Die Realisierung klebbarer Filme gelingt über die Auftragung von polymeren Dünnfilmen durch Spin-Coating des jeweiligen Monomeren. Diese Filme werden hinsichtlich ihrer Klebeeigenschaften charakterisiert. Abschließend werden alternative Kontaktiermethoden wie die Thermokompression oder das nanoskalige Löten basierend auf der Herstellung von segmentierten Nanodrähten demonstriert und hinsichtlich ihrer Applizierbarkeit diskutiert. Die erreichten Ergebnisse zeigen den noch vorhandenen Bedarf an technologischer Optimierung sowie Kompatibilisierung auf. Die Erkenntnisse hinsichtlich der Herstellung, des Wachstums sowie der Implementierungsansätze sind jedoch vielversprechend.

Colloidal semiconductor nanocrystals (NCs) have attracted a great deal of interest as bright and stable chromophores for a variety of applications. Their superior physicochemical properties depend on characteristics of the inorganic core, as well as on the chemical nature and structure of the stabilizing organic ligand shell. To evaluate the promising material, a thorough knowledge of structure-property relationships is still demanded. The present work addresses this challenge to three water-soluble NC systems, namely thiol-capped CdTe, thiol-capped CdHgTe, and DNA-functionalized CdTe NCs with special emphasis on the investigation of structure, modification, and influence of the ligand shell. Remarkably, CdTe NCs show bright emission in the visible spectral region and can be synthesized in high quality directly in water. It was shown that the aqueous synthesis also facilitates the preparation of strongly near-infrared (NIR) emitting CdHgTe NCs. The current work presents a detailed study on parameters, by which the emission can be tuned, such as the growth time, the initial Cd : Hg ratio, and the choice of ligand. These insights contribute to the knowledge, which is essential for the design of highly emissive and long-term stable NIR emitting NCs. Further variations of the NC/ligand system include the modification of the ligand shell of CdTe NCs with oligonucleotides based on the strong attachment of DNA molecules to the NC. The successful functionalization of NCs with single-stranded DNA molecules is very promising for the precise and programmable assembly of NCs using DNA origami structures as templates. For both, functionality and optical properties, the surface chemistry of the NCs plays a substantial role and was subject to an extensive investigation. As there is no generally applicable technique to determine the amount of stabilizers and the structure of the ligand shell, the presented study is based on a combination of various methods particularly tailored to the analysis of water-soluble CdTe NCs capped by short-chain thiols. CdTe NCs served as a model system for the described analysis of the ligand shell, since they are thoroughly studied regarding synthesis and features of the core. Aiming for the quantification of thiols, a straightforward colorimetric assay, the Ellman\'s test, is for the first time introduced for the analysis of NCs. Accompanied by elemental analysis an approximate number of thiols per NC becomes accessible. Moreover, theoretical calculations were performed to estimate the amount of ligand that would cover the NC in a monolayer of covalently bound molecules. In contrast to these results, the experimental values point to a larger amount of thiols immobilized on the NC. Attempts to remove the ligand indicate the presence of Cd in the ligand shell and thermogravimetric studies show that the ligands are not loosely assembled in the ligand shell. The outstanding conclusion of these findings involves the presence of Cd-thiol complexes in the ligand shell. Further results unambiguously show that the amount of Cd-thiol complexes present in the NC solution strongly influences the concentration-dependent emission yield of the NCs. Additional studies dedicated to the considerable influence of the ligand shell highlight a strong effect of pH, NC concentration, type and purity of the solvent, and the number of precipitation steps on the emission of water-soluble semiconductor NCs. These substantial investigations emphasize the need to carefully control the conditions applied for handling, optical measurements, and application of NCs. In order to gain a deeper insight into the complex structure of the native ligand shell, techniques deliberately chosen for the in situ analysis were applied for thioglycolic acid-capped CdTe NCs. Information from dynamic light scattering (DLS) regarding the stability and the shell thickness are consistent with previous results showing a large ligand network on the NC surface and a decreasing stability of the NCs upon dilution. Importantly, nuclear magnetic resonance (NMR) spectroscopy allows for the distinction of bound and free ligands directly in solution and proves the presence of these species for the NCs studied. In particular, the results indicate that the ligands are not strongly bound to the NC core and that both, free and bound ligand species, consist of modified thiol molecules, such as Cd-thiol complexes. These findings support previous assumptions and allow to establish a distinct picture of the ligand shell of water-soluble semiconductor NCs. Further insights were obtained from small-angle X-ray scattering (SAXS), which facilitates the identification and the determination of the composition of NC core as well as ligand shell. Element-specific SAXS yields the final proof of the presence of Cd in the ligand shell. The model developed for the optimal fitting of the experimental scattering curves additionally confirms the findings from the other methods. In conclusion, the present work contributes to the challenging goal of a comprehensive knowledge of interactions between the NC core and the ligands. The fundamental development of a structural model of water-soluble CdTe NCs including information on stoichiometries is accomplished by the combination of the techniques presented and emphasizes the challenge to assign a clear border between the ligand shell and the Cd-thiol complexes in solution. Altogether, CdTe NCs capped by thioglycolic acid are best described by a crystalline core surrounded by a water-swollen Cd-thiolate shell that considerably affects the optical properties of the system. Notably, the results of the versatile study provide the opportunity to control the overall properties and to evaluate water-soluble semiconductor NCs for particular applications in photonics and optoelectronics.

Multi-metallic aerogels have recently emerged as a novel and promising class of unsupported electrocatalyst materials due to their high catalytic activity and improved durability for various electrochemical reactions. Aerogels can be prepared by a spontaneous one-step gelation process, where the chemical co-reduction of metal precursors and the prompt formation of nanochain-containing hydrogels, as a preliminary stage for the preparation of aerogels, take place. However, detailed knowledge about the homogeneity and chemical distribution of these three-dimensional Pd–Pt aerogels at the nano-scale as well as at the macro-scale is still unclear. Therefore, we used a combination of spectroscopic and microscopic techniques to obtain a better insight into the structure and elemental distribution of the various Pd-rich Pd–Pt aerogels prepared by the spontaneous one-step gelation process. Synchrotron-based extended X-ray absorption fine structure (EXAFS) spectroscopy and high-angle annular dark-field (HAADF) scanning transmission electron microscopy (STEM) in combination with energy-dispersive X-ray spectroscopy (EDX) were employed in this work to uncover the structural architecture and chemical composition of the various Pd-rich Pd–Pt aerogels over a broad length range. The Pd80Pt20, Pd60Pt40 and Pd50Pt50 aerogels showed heterogeneity in the chemical distribution of the Pt and Pd atoms inside the macroscopic nanochain-network. The features of mono-metallic clusters were not detected by EXAFS or STEM-EDX, indicating alloyed nanoparticles. However, the local chemical composition of the Pd–Pt alloys strongly varied along the nanochains and thus within a single aerogel. To determine the electrochemically active surface area (ECSA) of the Pd–Pt aerogels for application in electrocatalysis, we used the electrochemical CO stripping method. Due to their high porosity and extended network structure, the resulting values of the ECSA for the Pd–Pt aerogels were higher than that for a commercially available unsupported Pt black catalyst. We show that the Pd–Pt aerogels possess a high utilization of catalytically active centers for electrocatalytic applications based on the nanostructured bimetallic framework. Knowledge about the homogeneity and chemical distribution of the bimetallic aerogels can help to further optimize their preparation by the spontaneous one-step gelation process and to tune their electrocatalytic reactivity.

Electronic Packaging is currently deeply in need of new solutions concerning vertical interconnection strategies. With respect to downscaling the geometrical limits, entering the nanoscale for first-level interconnects is nothing more than a consequence. This thesis proposes a new strategy for highly resolved vertical interconnects that are realized by metallic nanowires (NWs). These are embedded inside a dielectric matrix enabling the further raster size reduction for chip interconnects. The creation of NW arrays in self-ordering templates (anodized Al2O3 (AAO) and track-etched poly carbonate) by electrochemical deposition of Ag and Ni inside the pores of these as well as the characterisation of the NWs' properties with respect to the film's applicability are to the fore. Electrical properties are shown to be sensitive to the mode of deposition. Crystallographic properties do not seem to be responsible for this while the NWs' morphology slightly differs and is therefore expected to remarkably influence electron transport. Additionally, the deposition mechanism in high-aspect-ratio pores of AAO is in another focus of investigation. This process was in the past described as diffusively controlled, but this assertion was not further evaluated. The presence of a gradient in the diffusion coefficient as well as the presence and expansion of an electrochemical double layer located at the template's inner surface are responsible limiting the deposition process. An existing model of porous electrodes is compared to the measured data and found not to be valid for the system of highly recessed ultramicroelectrode arrays by which this system is described. Therefore a new model that differentiates between charge-transfer and diffusive motion is proposed and shown to fit to the system's properties. Apart from mechanistic investigations, the implementation of the obtained NW arrays as an interconnector film proposes these to be applied best by adhesive bonding. Bonding properties were found to be well realizable by the additional coverage of the filled membranes with a polymer thin film. This can easily be attached onto the film by spin-coating the corresponding monomer and reactive curing while already being embedded in the package. Alternative methods for contact formation, such as non-reactive bonding and nanosoldering using segmented NWs, are proposed. The strategy is shown to still lack important technological questions while the findings with respect to fabrication, growth and implementation are very promising.:List of Figures List of Tables List of Acronyms List of Symbols 1 Nanoscale interconnects 1 1.1 Introduction 1.2 Electronic device development and its consequences 1.3 The need for and the design of a nanoscale wiring film 1.3.1 Nanomaterials for packaging - Some examples 1.3.2 Preconsiderations for designing nanoscale interconnects 1.3.3 Compatitibility of ACANWF to industrial applications 1.3.4 Demands to the film 1.4 Resumée - Strategy 2 NW fabrication by electodeposition and synthesis-property relationships 2.1 Templates for NW electrodeposition 2.1.1 Anodized Al2O3 (AAO) 2.1.2 Track-etched polymer membranes 2.2 Template-assisted Electrochemical Deposition (ECD) of NWs 2.2.1 Concept 2.2.2 Deposition modes 2.2.3 In_uences of other physical parameters 2.2.4 Errors and error mechanisms 2.2.5 Deposition in chemically functionalized AAO 2.3 Synthesis-property relationships for single NWs 2.3.1 NiNWs 2.3.2 AgNWs 2.4 Resumée . 3 Growth processes in mesoporous templates 3.1 Relevance for mechanistic investigations 3.2 Processes during NW growth 3.2.1 Electrode kinetics 3.2.2 Diffusion 3.2.3 Interactions with pore walls 3.3 Model systems 3.3.1 DeLevie's model for porous electrodes 3.3.2 Model verification 3.3.3 Model adaptation to non-ideal behaviour 3.4 Resumée 4 Implementation of nanowire arrays into microelectronic packaging 4.1 Adhesive Bonding 4.1.1 Adhesion by thin adhesive layers 4.1.2 Thermocompression bonds 4.2 Nanosoldering 4.2.1 Deposition of low melting point materials 4.2.2 Segmented nanowires 4.3 Resumée 5 Conclusion and perspectives 5.1 Conclusion 5.2 Perspectives on further investigations 6 Appendices 6.1 Technical equipment 6.2 Experimental methods 6.3 Selected characterisation techniques 6.4 Supplementary Information 6.5 Glossary 6.6 List of publications & presentations Bibliography / Die Aufbau- und Verbindungstechnik der Elektronik wird in absehbarer Zeit Größenskalen erreichen, bei denen die verwendeten Materialien in der ersten Kontaktierungsebene als Nanomaterialien zu bezeichnen sind, das heißt ≤ 100 nm sind. Des Weiteren bestehen momentan nur bedingt viele Ansätze zu deren Implementierung in Vertikalverbindungsstrukturen (zum Beispiel für die dreidimensionale Integration). Die vorliegende Dissertation schlägt daher vor, die vertikale Verbindung über einen zwischen die Chips laminierbaren Film mit hochdichten und vertikal ausgerichteten nanoskaligen Drähten (NWs) zu realisieren. Diese sind in einer dielektrischen Matrix fixiert und gewährleisten die elektrische Anisotropie des Kontaktfilms. Innerhalb dieser Matrix werden die metallischen Drähte durch elektrochemische Abscheidung erzeugt. Der Fokus dieser Arbeit liegt somit auf der Charakterisierung des reduktiven Wachstumsprozesses von Ag und Ni innerhalb dünner Poren. Dabei können die Eigenschaften durch verschiedene Abscheidemodi gezielt beeinflusst werden. Hinsichtlich der elektrischen Eigenschaften ergibt sich im Vergleich zu der zugrundeliegenden Kristallographie ein wesentlich stärkerer Einfluss der Draht-Morphologie. Der Prozess der Porenfüllung wird im Allgemeinen als stark diffusionskontrolliert angenommen, wurde jedoch bisher nicht weiter quantifiziert. Die der Abscheidung zugrundeliegenden Prozesse Elektrolytdiffusion, Ladungstransfer an der Elektrode und Migrationsbeeinflussung durch die Porengeometrie werden daher voneinander getrennt und einzeln charakterisiert. Das vorliegende System kann als Matrix von stark versenkten Ultramikroelektroden abstrahiert werden. Existente Modelle zur Beschreibung derartiger Systeme treffen auf den vorliegenden Fall im Allgemeinen nicht zu, sodass basierend auf elektrochemischen Untersuchungen ein variiertes Abscheidemodell vorgeschlagen wird. Dieses berücksichtigt die Nicht-Linearität der elektrochemischen Doppelschicht, die von der Porenoberfläche ausgeht sowie deren Frequenzabhängigkeit. Neben mechanistischen Untersuchungen schließen sich Versuche an, deren Fokus auf der direkten Anwendung der mit Nanodrähten gefüllten Membranen liegt. Dabei wird vornehmlich deren Fixierung per Klebeverbindung angestrebt. Die Realisierung klebbarer Filme gelingt über die Auftragung von polymeren Dünnfilmen durch Spin-Coating des jeweiligen Monomeren. Diese Filme werden hinsichtlich ihrer Klebeeigenschaften charakterisiert. Abschließend werden alternative Kontaktiermethoden wie die Thermokompression oder das nanoskalige Löten basierend auf der Herstellung von segmentierten Nanodrähten demonstriert und hinsichtlich ihrer Applizierbarkeit diskutiert. Die erreichten Ergebnisse zeigen den noch vorhandenen Bedarf an technologischer Optimierung sowie Kompatibilisierung auf. Die Erkenntnisse hinsichtlich der Herstellung, des Wachstums sowie der Implementierungsansätze sind jedoch vielversprechend.:List of Figures List of Tables List of Acronyms List of Symbols 1 Nanoscale interconnects 1 1.1 Introduction 1.2 Electronic device development and its consequences 1.3 The need for and the design of a nanoscale wiring film 1.3.1 Nanomaterials for packaging - Some examples 1.3.2 Preconsiderations for designing nanoscale interconnects 1.3.3 Compatitibility of ACANWF to industrial applications 1.3.4 Demands to the film 1.4 Resumée - Strategy 2 NW fabrication by electodeposition and synthesis-property relationships 2.1 Templates for NW electrodeposition 2.1.1 Anodized Al2O3 (AAO) 2.1.2 Track-etched polymer membranes 2.2 Template-assisted Electrochemical Deposition (ECD) of NWs 2.2.1 Concept 2.2.2 Deposition modes 2.2.3 In_uences of other physical parameters 2.2.4 Errors and error mechanisms 2.2.5 Deposition in chemically functionalized AAO 2.3 Synthesis-property relationships for single NWs 2.3.1 NiNWs 2.3.2 AgNWs 2.4 Resumée . 3 Growth processes in mesoporous templates 3.1 Relevance for mechanistic investigations 3.2 Processes during NW growth 3.2.1 Electrode kinetics 3.2.2 Diffusion 3.2.3 Interactions with pore walls 3.3 Model systems 3.3.1 DeLevie's model for porous electrodes 3.3.2 Model verification 3.3.3 Model adaptation to non-ideal behaviour 3.4 Resumée 4 Implementation of nanowire arrays into microelectronic packaging 4.1 Adhesive Bonding 4.1.1 Adhesion by thin adhesive layers 4.1.2 Thermocompression bonds 4.2 Nanosoldering 4.2.1 Deposition of low melting point materials 4.2.2 Segmented nanowires 4.3 Resumée 5 Conclusion and perspectives 5.1 Conclusion 5.2 Perspectives on further investigations 6 Appendices 6.1 Technical equipment 6.2 Experimental methods 6.3 Selected characterisation techniques 6.4 Supplementary Information 6.5 Glossary 6.6 List of publications & presentations Bibliography

Colloidal semiconductor nanocrystals (NCs) have attracted a great deal of interest as bright and stable chromophores for a variety of applications. Their superior physicochemical properties depend on characteristics of the inorganic core, as well as on the chemical nature and structure of the stabilizing organic ligand shell. To evaluate the promising material, a thorough knowledge of structure-property relationships is still demanded. The present work addresses this challenge to three water-soluble NC systems, namely thiol-capped CdTe, thiol-capped CdHgTe, and DNA-functionalized CdTe NCs with special emphasis on the investigation of structure, modification, and influence of the ligand shell. Remarkably, CdTe NCs show bright emission in the visible spectral region and can be synthesized in high quality directly in water. It was shown that the aqueous synthesis also facilitates the preparation of strongly near-infrared (NIR) emitting CdHgTe NCs. The current work presents a detailed study on parameters, by which the emission can be tuned, such as the growth time, the initial Cd : Hg ratio, and the choice of ligand. These insights contribute to the knowledge, which is essential for the design of highly emissive and long-term stable NIR emitting NCs. Further variations of the NC/ligand system include the modification of the ligand shell of CdTe NCs with oligonucleotides based on the strong attachment of DNA molecules to the NC. The successful functionalization of NCs with single-stranded DNA molecules is very promising for the precise and programmable assembly of NCs using DNA origami structures as templates. For both, functionality and optical properties, the surface chemistry of the NCs plays a substantial role and was subject to an extensive investigation. As there is no generally applicable technique to determine the amount of stabilizers and the structure of the ligand shell, the presented study is based on a combination of various methods particularly tailored to the analysis of water-soluble CdTe NCs capped by short-chain thiols. CdTe NCs served as a model system for the described analysis of the ligand shell, since they are thoroughly studied regarding synthesis and features of the core. Aiming for the quantification of thiols, a straightforward colorimetric assay, the Ellman\'s test, is for the first time introduced for the analysis of NCs. Accompanied by elemental analysis an approximate number of thiols per NC becomes accessible. Moreover, theoretical calculations were performed to estimate the amount of ligand that would cover the NC in a monolayer of covalently bound molecules. In contrast to these results, the experimental values point to a larger amount of thiols immobilized on the NC. Attempts to remove the ligand indicate the presence of Cd in the ligand shell and thermogravimetric studies show that the ligands are not loosely assembled in the ligand shell. The outstanding conclusion of these findings involves the presence of Cd-thiol complexes in the ligand shell. Further results unambiguously show that the amount of Cd-thiol complexes present in the NC solution strongly influences the concentration-dependent emission yield of the NCs. Additional studies dedicated to the considerable influence of the ligand shell highlight a strong effect of pH, NC concentration, type and purity of the solvent, and the number of precipitation steps on the emission of water-soluble semiconductor NCs. These substantial investigations emphasize the need to carefully control the conditions applied for handling, optical measurements, and application of NCs. In order to gain a deeper insight into the complex structure of the native ligand shell, techniques deliberately chosen for the in situ analysis were applied for thioglycolic acid-capped CdTe NCs. Information from dynamic light scattering (DLS) regarding the stability and the shell thickness are consistent with previous results showing a large ligand network on the NC surface and a decreasing stability of the NCs upon dilution. Importantly, nuclear magnetic resonance (NMR) spectroscopy allows for the distinction of bound and free ligands directly in solution and proves the presence of these species for the NCs studied. In particular, the results indicate that the ligands are not strongly bound to the NC core and that both, free and bound ligand species, consist of modified thiol molecules, such as Cd-thiol complexes. These findings support previous assumptions and allow to establish a distinct picture of the ligand shell of water-soluble semiconductor NCs. Further insights were obtained from small-angle X-ray scattering (SAXS), which facilitates the identification and the determination of the composition of NC core as well as ligand shell. Element-specific SAXS yields the final proof of the presence of Cd in the ligand shell. The model developed for the optimal fitting of the experimental scattering curves additionally confirms the findings from the other methods. In conclusion, the present work contributes to the challenging goal of a comprehensive knowledge of interactions between the NC core and the ligands. The fundamental development of a structural model of water-soluble CdTe NCs including information on stoichiometries is accomplished by the combination of the techniques presented and emphasizes the challenge to assign a clear border between the ligand shell and the Cd-thiol complexes in solution. Altogether, CdTe NCs capped by thioglycolic acid are best described by a crystalline core surrounded by a water-swollen Cd-thiolate shell that considerably affects the optical properties of the system. Notably, the results of the versatile study provide the opportunity to control the overall properties and to evaluate water-soluble semiconductor NCs for particular applications in photonics and optoelectronics.

Colloidal semiconductor quantum dots (QDs) have gained substantial interest as adjustable, bright and spectrally tunable fluorophores in the past decades. Besides their in-depth analyses in the scientific community, first industrial applications as color conversion and color enrichment materials were implemented. However, stability and processability are essential for their successful use in these and further applications. Methods to embed QDs into oxides or polymers can only partially solve this challenge. Recently, our group introduced the embedding of QDs into ionic salts, which holds several advantages in comparison to polymer or oxide-based counterparts. Both gas permeability and environmental-related degradation processes are negligible, making these composites an almost perfect choice of material. To evaluate this new class of QD-salt mixed crystals, a thorough understanding of the formation procedure and the final composites is needed. The present work is focused on embedding both aqueous-based and oil-based metal-chalcogenide QDs into several ionic salts and the investigations of their optical and chemical properties upon incorporation into the mixed crystals. QDs with well-known, reproducible and high-quality synthetic protocols are chosen as emissive species. CdTe QDs were incorporated into NaCl as host matrix by using the straightforward "classical" method. The resulting mixed crystals of various shapes and beautiful colors preserve the strong luminescence of the incorporated QDs. Besides NaCl, also borax and other salts are used as host matrices. Mercaptopropionic acid stabilized CdTe QDs can easily be co-crystallized with NaCl, while thioglycolic acid as stabilizing agent results in only weakly emitting powder-like mixed crystals. This challenge was overcome by adjusting the pH, the amount of free stabilizer and the type of salt used, demonstrating the reproducible incorporation of highest-quality CdTe QDs capped with thioglycolic acid into NaCl and KCl salt crystals. A disadvantage of the "classical" mixed crystallization procedure was its long duration which prevents a straightforward transfer of the protocol to less stable QD colloids, e.g., initially oil-based, ligand exchanged QDs. To address this challenge, the "Liquid-liquid-diffusion-assisted-crystallization" (LLDC) method is introduced. By applying the LLDC, a substantially accelerated ionic crystallization of the QDs is shown, reducing the crystallization time needed by one order of magnitude. This fast process opens the field of incorporating ligand-exchanged Cd-free QDs into NaCl matrices. To overcome the need for a ligand exchange, the LLDC can also be extended towards a two-step approach. In this modified version, the seed-mediated LLDC provides for the first time the ability to incorporate oil-based QDs directly into ionic matrices without a prior phase transfer. The ionic salts appear to be very tight matrices, ensuring the protection of the QDs from the environment. As one of the main results, these matrices provide extraordinary high photo- and chemical stability. It is further demonstrated with absolute measurements of photoluminescence quantum yields (PL-QYs), that the PL-QYs of aqueous CdTe QDs can be considerably increased upon incorporation into a salt matrix by applying the "classical" crystallization procedure. The achievable PL enhancement factors depend strongly on the PL-QYs of the parent QDs and can be described by the change of the dielectric surrounding as well as the passivation of the QD surface. Studies on CdSe/ZnS in NaCl and CdTe in borax showed a crystal-induced PL-QY increase below the values expected for the respective change of the refractive index, supporting the derived hypothesis of surface defect curing by a CdClx formation as one main factor for PL-QY enhancement. The mixed crystals developed in this work show a high suitability as color conversion materials regarding both their stability and spectral tunability. First proof-of-concept devices provide promising results. However, a combination of the highest figures of merit at the same time is intended. This ambitious goal is reached by implementing a model-experimental feedback approach which ensures the desired high optical performance of the used emitters throughout all intermediate steps. Based on the approach, a white LED combining an incandescent-like warm white with an exceptional high color rendering index and a luminous efficacy of radiation is prepared. It is the first time that a combination of this highly related figures of merit could be reached using QD-based color converters. Furthermore, the idea of embedding QDs into ionic matrices gained considerable interest in the scientific community, resulting in various publications of other research groups based on the results presented here. In summary, the present work provides a profound understanding how this new class of QD-salt mixed crystal composites can be efficiently prepared. Applying the different crystallization methods and by changing the matrix material, mixed crystals emitting from blue to the near infrared region of the electromagnetic spectrum can be fabricated using both Cd-containing and Cd-free QDs. The resulting composites show extraordinary optical properties, combining the QDs spectral tunability with the rigid and tight ionic matrix of the salt. Finally, their utilization as a color conversion material resulted in a high-quality white LED that, for the first time, combines an incandescent-like hue with outstanding optical efficacy and color rendering properties. Besides that, the mixed crystals offer huge potential in other high-quality applications which apply photonic and optoelectronic components.

Inhalt der Arbeit ist die Synthese und Charakterisierung von Hydrogelen auf Stärkebasis mit dem Ziel, diese für unterschiedliche Anwendungszwecke, insbesondere jedoch als Kontaktmedium in der medizinischen Ultraschalldiagnostik, einsetzen zu können. Um Stärke zur Ausbildung stabiler, wässriger Gele zu befähigen, werden mehrere Funktionalisierungsschritte vollzogen. Die Einführung von Carboxymethylfunktionen mittels Williamson-Reaktion erhöht den ionischen Charakter und damit die Hydrophilie des Biopolymers. Zur kinetischen Beschreibung der Carboxymethylierung am Stärkekorn in Suspension wird ein Dreiphasenmodell eingeführt. Der Aufbau eines für Gelstrukturen charakteristischen, dreidimensionalen Netzwerks erfolgt durch inter- und intramolekulare Verknüpfung einzelner Polymerstränge über kovalente Etherbrücken. Durch Eliminierung der nach Substitution und Vernetzung löslich verbliebenen Polymeranteile können die Materialeigenschaften des gequollenen Hydrogels erheblich verbessert werden. Rheologische Messungen und bildgebende Untersuchungen mit Gewebephantomen qualifizieren Stärke-Gele als in anwendungstechnischer Hinsicht geeignetes Kontaktmedium in der medizinischen Ultraschalldiagnostik. Mit speziellen Tests wird die pharmakologisch-toxikologische Unbedenklichkeit der Produkte nachgewiesen.

Surface-enhanced Raman scattering (SERS) microscopy is a novel method of optical imaging for the localization and quantification of target molecules in cells and tissue specimens. The major advantages of SERS over fluorescence are quantification and spectral multiplexing due to the small line width of vibrational Raman bands. The position of the plasmon band of both hollow gold/silver nanoshells and silica-encapsulated gold nanoclusters can be tuned for maximum SERS enhancement upon red laser excitation, which is optimal for minimizing the disturbing autofluorescence of tissue. In this work, silica-encapsulated and non-encapsulated SERS particles were used for the localization of target proteins in prostate tissue specimens. Two different biofunctionalization methods were established for each type of SERS particles. The cross-linking method based on s-NHS/EDC chemistry was modified for covalently conjugating proteins to hollow gold/silver nanoshells and gold nanostars in order to minimize the aggregation of SERS nanoparticles during and after cross-linking. As an alternative to covalent conjugation chemistry, the noncovalent binding of antibodies to the SERS particles via an adapter protein (protein A/G) was established. The influence of several factors that determine the quality of results obtained by SERS imaging, such as the number of immuno-SERS conjugates, incubation time, antigen retrieval and blocking buffer, were investigated. Rapid SERS microscopy with 30 msec acquisition time per pixel was enabled by using silica-encapsulated gold nanoclusters for the localization of p63 proteins on prostate tissue specimens from healthy donors. Two-color SERS experiments for the parallel localization of PSA and p63 were performed with silica-encapsulated and non-encapsulated nanoshells. The quality of the results depends less on the nature of the surface chemistry of the nanoparticles (with or without silica encapsulation), but more on the blocking buffer and the antigen retrieval method. Silica-encapsulated gold nanoclusters were also used for the simultaneous quantification of three cytokines (IL1, IL8 and TNF- α) in a SERS-based sandwich immunoassay with a detection limit of ca. 0.3 pM. Keywords: Raman, SERS microscopy, biocompatibility of nanoparticles, cross-linking, antigen unmasking methods, antigen detection, immunohistochemistry, immunoassay.