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Silicon Nanoparticle Synthesis and Modeling for Thin Film Solar CellsAlbu, Zahra 30 April 2014 (has links)
Nanometer-scale silicon shows extraordinary electronic and optical properties that
are not available for bulk silicon, and many investigations toward applications in optoelectronic
devices are being pursued. Silicon nanoparticle films made from solution
are a promising candidate for low-cost solar cells. However, controlling the properties
of silicon nanoparticles is quite a challenge, in particular shape and size distribution,
which effect device performance. At present, none of the solar cells made from silicon
nanoparticle films have an efficiency exceeding the efficiency of those based on crystalline
silicon. To address the challenge of controlling silicon nanoparticle properties,
both theoretical and experimental investigations are needed. In this thesis, we investigate
silicon nanoparticle properties via quantum mechanical modeling of silicon
nanoparticles and synthesis of silicon nanoparticle films via colloidal grinding.
Silicon nanoparticles with shapes including cubic, rectangular, ellipsoidal and flat
disk are modeled using semi-empirical methods and configuration interaction. Their
electronic properties with different surface passivation were also studied. The results
showed that silicon nanoparticles with hydrogen passivation have higher HOMOLUMO
gaps, and also the HOMO-LUMO gap depends on the size and the shape
of the particle. In contrast, silicon nanoparticles with oxygen passivation have a
lower HOMO-LUMO gap. Raman spectroscopy calculation of silicon nanoparticles
show peak shift and asymmetric broadening similar to what has been observed in
experiment.
Silicon nanoparticle synthesis via colloidal grinding was demonstrated as a straightforward
and inexpensive approach for thin film solar cells. Data analysis of silicon
particles via SEM images demonstrated that colloidal grinding is effective in reducing
the Si particle size to sub-micron in a short grinding time. Further increases in
grinding time, followed by filtration demonstrated a narrowing of the Si particle size
and size-distribution to an average size of 70 nm. Raman spectroscopy and EDS data
demonstrated that the Si nanoparticles contain oxygen due to exposure to air during
grinding. I-V characterization of the milled Si nanoparticles showed an ohmic behaviour
with low current at low biases then Schottky diode behaviour or a symmetric
curve at large biases. / Graduate / 0794 / 0544 / zahraalbu@hotmail.com
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Silicon Nanoparticle Synthesis and Modeling for Thin Film Solar CellsAlbu, Zahra 30 April 2014 (has links)
Nanometer-scale silicon shows extraordinary electronic and optical properties that
are not available for bulk silicon, and many investigations toward applications in optoelectronic
devices are being pursued. Silicon nanoparticle films made from solution
are a promising candidate for low-cost solar cells. However, controlling the properties
of silicon nanoparticles is quite a challenge, in particular shape and size distribution,
which effect device performance. At present, none of the solar cells made from silicon
nanoparticle films have an efficiency exceeding the efficiency of those based on crystalline
silicon. To address the challenge of controlling silicon nanoparticle properties,
both theoretical and experimental investigations are needed. In this thesis, we investigate
silicon nanoparticle properties via quantum mechanical modeling of silicon
nanoparticles and synthesis of silicon nanoparticle films via colloidal grinding.
Silicon nanoparticles with shapes including cubic, rectangular, ellipsoidal and flat
disk are modeled using semi-empirical methods and configuration interaction. Their
electronic properties with different surface passivation were also studied. The results
showed that silicon nanoparticles with hydrogen passivation have higher HOMOLUMO
gaps, and also the HOMO-LUMO gap depends on the size and the shape
of the particle. In contrast, silicon nanoparticles with oxygen passivation have a
lower HOMO-LUMO gap. Raman spectroscopy calculation of silicon nanoparticles
show peak shift and asymmetric broadening similar to what has been observed in
experiment.
Silicon nanoparticle synthesis via colloidal grinding was demonstrated as a straightforward
and inexpensive approach for thin film solar cells. Data analysis of silicon
particles via SEM images demonstrated that colloidal grinding is effective in reducing
the Si particle size to sub-micron in a short grinding time. Further increases in
grinding time, followed by filtration demonstrated a narrowing of the Si particle size
and size-distribution to an average size of 70 nm. Raman spectroscopy and EDS data
demonstrated that the Si nanoparticles contain oxygen due to exposure to air during
grinding. I-V characterization of the milled Si nanoparticles showed an ohmic behaviour
with low current at low biases then Schottky diode behaviour or a symmetric
curve at large biases. / Graduate / 0794 / 0544 / zahraalbu@hotmail.com
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Direct Synthesis of Thiolate-Protected Gold Nanoparticles Using Bunte Salts as Ligand Precursors: Investigations of Ligand Shell Formation and Core Growth / Investigations of Ligand Shell Formation and Core GrowthLohse, Samuel E., 1981- 06 1900 (has links)
xx, 242 p. : ill. (some col.) / Applications of ligand-protected nanoparticles have increased markedly in recent years, yet their controlled synthesis remains an under-developed field. Nanoparticle syntheses are highly specialized in their execution and often possess significant limitations. For example, the synthesis of thiol-stabilized gold nanoparticles (AuNPs) with core diameters greater than 5.0 nm is difficult to achieve using existing methods. This dissertation describes the development of a synthetic strategy for thiolate-stabilized AuNPs over a wide range of core sizes using alkyl thiosulfates (Bunte salts) as ligand precursors. The use of Bunte salts permits the synthesis of larger AuNPs than can be achieved using thiols by allowing the AuNP cores to grow to larger diameters before the formation of the thiolate ligand shell. Chapter II details the development of a direct synthesis strategy using Bunte salts as ligand precursors that produces AuNPs with diameters up to 20 nm. Chapter III describes an investigation of the ligand shell formation that occurs during these syntheses. The ligand shell formation involves the adsorption of the Bunte salt to the AuNP surface, where it is converted to the thiolate. This conversion requires an excess of sodium borohydride in the synthesis of >5 nm AuNPs, but not for the synthesis of smaller AuNPs. This synthetic strategy was adapted for use in flow reactors to attain simultaneous AuNP synthesis and characterization. Chapter IV demonstrates that thiol-stabilized AuNPs can be synthesized in a microfluidic device with product monitoring provided by UV-vis absorbance spectroscopy. The development of a capillary flow reactor that permits the incorporation of new monitoring techniques is presented in Chapter V. The incorporation of Small-Angle X-ray Scattering (SAXS) analysis provides quantitative <italic>in situ</italic> determinations of AuNP diameter. The combination of synthetic control and monitoring makes capillary flow reactors powerful tools for optimization of NP syntheses and monitoring NP growth. In Chapter VI, the capillary flow reactor is used in an investigation of AuNP core growth. We also review AuNP growth mechanisms and show how to differentiate these using SAXS and UV-vis analysis. In these studies, AuNP growth is unexpectedly shown to involve a coalescence mechanism. This dissertation includes previously published and co-authored material. / Committee in charge: Victoria De Rose Chairperson;
James E. Hutchison, Advisor;
Catherine Page, Member;
Darren W. Johnson, Member;
Miriam Deutsch, Outside Member
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SYNTHESIS AND OPTICAL PROPERTIES OF ULTRAFINE METAL NANOPARTICLES ON DIELECTRIC ANTENNA PARTICLESWei, Qilin, 0000-0003-1729-1951 January 2022 (has links)
Effective light energy conversion into other forms of energy in metal and metal compound nanoparticles has been of great interest in past decades. Being illuminated by incident light, electrons in the nanoparticles can be excited to higher energy states followed by deposition of energy into other molecules around their surface and the lattices in the following relaxation process. Ultrafine nanoparticles are thus preferred in these processes due to their high specific surface areas. Moreover, the portion of excited electrons with higher energies is higher in smaller nanoparticles than in larger ones. However, the overall light power absorbed by nanoparticles is proportional to the square of particle size, which causes the ultrafine nanoparticles not to efficiently absorb the incident light, or to drive further chemical or physical processes.Light antennae materials are usually employed to enhance the light absorption of these ultrafine nanoparticles. Plasmonic nanoparticles, e.g., Ag, Au, Cu, and Al nanoparticles, enhance the light absorption of loaded nanoparticles mainly through strong electromagnetic fields generated near their surfaces and have been proven to be effective light antennae to benefit the light energy conversion of ultrafine nanoparticles. On the other hand, spherical dielectric particles, e.g., silicon dioxide nanospheres, represent a different type of light antennae with the advantages of low cost, simple synthesis, and negligible Ohmic loss when being illuminated. When the sizes of high geometric symmetry dielectric nanospheres are comparable with the wavelength of the incident light, Mie scattering can happen based on the difference in refractive index between the sphere and the surrounding medium, generating size-dependent scattering resonances at various wavelengths. At these wavelengths, strong electric fields can be created on the surface of dielectric spheres to enhance the light absorption of the nanoparticles loaded on the surface. Previous works have shown that silica nanospheres with a diameter of several hundreds of nanometers can effectively enhance the light absorption of ultrafine Pt nanoparticles and benefit photocatalytic reactions, e.g., selective oxidation of benzyl alcohol. Over the past few years, this concept has been broadened to other ultrafine nanoparticles to study their novel photo-to-chemical/physical properties. However, the availability and comprehensive understanding of the optical properties of this class of composite particles still need to be improved. These challenges limit the further development of these composite materials in new light energy conversion processes. This dissertation aims at studying this class of novel ultrafine nanoparticles/dielectric sphere composite particles synthesis and optical properties.
In Chapter 2, a synthesis protocol of ultrafine ruthenium oxyhydroxide nanoparticles on the surface of silica nanospheres’ surfaces is introduced. Unlike the traditional synthesis of nanoparticles in solution followed by a loading process, the method developed in this chapter only requires the injection of aqueous ruthenium salt solution into a silica nanosphere dispersion. The obtained ultrafine nanoparticles with sizes of 2-3 nm are characterized to be ruthenium oxyhydroxide (RuOOH) nanoparticles. The silica nanospheres are crucial in stabilizing these ultrafine RuOOH nanoparticles and enhancing their light absorption. Due to the presence of ruthenium-oxygen bonds in the nanoparticles, the absorbed photons are converted to heat and transferred to the surrounding media with a photo-to-thermal conversion efficiency close to the unity. Experimental results have shown that heat can be effectively used in accelerating the reaction rate of selective oxidation of benzyl alcohol by molecular oxygen. Kinetics data also have shown that these ultrafine RuOOH nanoparticles are able to activate molecular oxygen adsorbed on their surfaces, which represents a novel property of these ultrafine RuOOH nanoparticles that is not observed in other traditional ruthenium catalysts.
In Chapter 3, a more general synthesis method of ultrafine metal and metal oxyhydroxide nanoparticles on silica nanospheres is developed, inspired by the synthetic route in Chapter 2. Instead of functionalizing silica surfaces with silane agents with amino groups, the silica surfaces are selectively etched by an aqueous base to create a high density of surface hydroxyl groups. These hydroxyl groups can provide basic sites to stabilize metal ions in aqueous dispersion, which are nuclei for the further growth of larger metal oxyhydroxide nanoparticles. In this chapter, more than ten kinds of metal ions are loaded onto silica spheres, forming oxyhydroxide nanoparticles with average sizes below 5 nm. Some oxyhydroxide nanoparticles can be reduced by 5% H2/N2 to form metal nanoparticles with their ultrafine sizes maintained. The synthesis protocol is promising in preparation of bimetallic samples. The composition and optical absorption of all obtained composite particles are analyzed, demonstrating the practicability of utilizing the reported method to prepare high-quality light-absorbing composite particles.
In Chapter 4, the optical absorption property of the composite particle is systematically studied. Using ultrafine Pt nanoparticles as the light absorbing material, the light absorptions of composite particles consisting of silica spheres with diameters from 100 to 1100 nm loaded with these Pt nanoparticles are studied. Through the combination of theoretical calculation based on Mie theory and the measured optical absorption spectra, the scattering resonance peaks are successfully located in each sample. It is also found that the photonic crystal effect and the general absorption of Pt nanoparticles can contribute to the light absorption spectra, especially at higher wavelengths. The relationship between the general absorption of Pt nanoparticles and the packing density of the powder is further studied. The successful deconvolution of several components in the absorption spectra can guide the further rational design of composite particles in optical-related applications.
In Chapter 5, the composite particle system is further broadened to using high refractive index zinc sulfide nanospheres as a light antenna. The use of a higher refractive index light antenna is promising for obtaining higher light absorption enhancement in loaded ultrafine nanoparticles, even though the sample is dispersed in organic media with a high refractive index as well. After the successful loading of Pt nanoparticles to the surface of silica-coated zinc sulfide nanospheres, a protocol for analyzing their light absorption spectra in organic media is proposed. Size-dependent scattering resonance peaks are observed in bare zinc sulfide nanospheres and can be utilized to enhance the light absorption of Pt nanoparticles, even when the sample is sealed in high refractive index polymeric matrices. The composite particles are further employed in photothermal tests, the results prove that the better light absorption enhancement using zinc sulfide than silica nanospheres.
The results introduced in this dissertation represent the first systematic and comprehensive study of ultrafine metal and metal oxyhydroxide nanoparticles loaded on the surface of dielectric light antenna particles. The conclusions open an avenue to further rational design of high-performance light-absorbing composite particles to be used in photo-to-thermal/chemical processes. / Chemistry
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A Study of Gold Nanoparticles for Application in Semiconductor CdS Nanosheet Biosensor DevicesGeitner, Nicholas 16 August 2011 (has links)
No description available.
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DEVELOPMENT OF AN AC-POWERED ATMOSPHERIC-PRESSURE, FLOWING MICROPLASMA FOR GAS-PHASE NANOPARTICLE SYNTHESISHuang, I-Min 09 February 2015 (has links)
No description available.
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Connecting Thermodynamics and Kinetics of Ligand Controlled Colloidal Pd Nanoparticle SynthesisLi, Wenhui 24 April 2019 (has links)
Colloidal nanoparticles are widely used for industrial and scientific purposes in many fields, including catalysis, biosensing, drug delivery, and electrochemistry. It has been reported that most of the functional properties and performance of the nanoparticles are highly dependent on the particle size and morphology. Therefore, controlled synthesis of nanomaterials with desired size and structure is greatly beneficial to the application.
This dissertation presents a systematic study on the effect of ligands on the colloidal Pd nanoparticle synthesis mechanism, kinetics, and final particle size. Specifically, the research is focused on investigating how the ligand bindings to different metal species, i.e., metal precursor and nanoparticle surface, affect the nucleation and growth pathways and rates and connecting the binding thermodynamics to the kinetics quantitatively. The first part of the work (Chapters 4 and 5) is establishing isothermal titration calorimetry (ITC) methodology for obtaining the thermodynamic values (Gibbs free energy, equilibrium constant, enthalpy and entropy) of the ligand-metal precursor binding reactions, and the simultaneous metal precursor trimer dissociation. In brief, the binding products and reactions were characterized by nuclear magnetic resonance (NMR), and an ITC model was developed to fit the unique ITC heat curve and extract the thermodynamic properties of the reactions above. Furthermore, in Chapter 6, the thermodynamic properties, especially the entropy trend changing with the ligand chain length was investigated on different metal precursors based on the established ITC methodology, showing that the entropic penalty plays a significant role in the binding equilibrium.
The second part of the dissertation (Chapter 7 and 8) presents the kinetic and mechanistic study on size-tuning of the colloidal Pd nanoparticles only by changing different coordinating solvents as ligands together with the trioctylphosphine ligand. In-situ small angle X-ray scattering was applied to characterize the time evolutions of size, size distribution, and particle concentration using synthesis reactor connected to a capillary flow cell. From the real-time kinetic measurements, the nucleation and growth rates were calculated and correlated with the thermodynamics, i.e., Gibbs free energies of solvent-ligand-metal precursor reactivity and ligand-nanoparticle surface binding which were modified by the coordination of different solvents. Higher reactivity leads to faster nucleation and high nanoparticle concentration, and stronger solvent/ligand-particle coordination energy results in higher ligand capping density and slower growth. The interplay of both effects reduces the final particle size. Furthermore, because of the significance of the ligand-metal interactions, the synthesis temperature and ligand to metal precursor ratio were systematically to modify the relative binding between the ligand and precursor, and the ligand and nanoparticle, and determine the effect on the nucleation and growth rates. The results show that the relative rates of nucleation and growth is critical to the final size. A methodology for using the in-situ measurements to predict the final size by developing a kinetic model based is discussed. / Doctor of Philosophy / Metal nanoparticles dispersed in solution phase, i.e., colloidal nanoparticles, are of great scientific interests due to their unique properties different from bulk metal materials. The size, shape and other morphology features can largely affect the nanomaterial properties and functional performances. Therefore, a successful synthesis of nanoparticles with desired structures is highly beneficial to the development of their application. Ligands, which are long-chain molecules that can cap on the surface of the nanoparticles, have been known as stabilizers of the nanoparticles in the solution phase. Whereas in recent studies, it has been found that changing the ligand type and concentration in the synthesis can result in different sizes and shapes of nanomaterials, which indicates that the ligands are playing critical roles in the synthesis mechanisms to control the kinetics.
To have a better understanding on the control effects of the ligands, systematic studies were conducted on the ligand interactions (bindings) between the ligand-metal compound (as the metal source and initial agent in the nanomaterial synthesis) and ligand-nanoparticle surface, of which both can be quantified by thermodynamics. Using isothermal titration calorimetry, the ligand-metal precursor binding strength was measured and found to be dependent on ligand chain length and the metal precursors, which further affects the reactivity of the metal precursor based on the results of density functional theory calculations. On the other hand, the ligand-nanoparticle surface binding strength was found to affect the capping density of the ligands on the nanoparticle surface.
In order to connect the thermodynamics to the kinetics, namely the nucleation (formation of new particles) and growth (particle size increase) rates, small angle X-ray scattering (SAXS) characterization was performed in real time during the synthesis on the nanoparticles. This technique allows the capture of the size, size distribution and concentration of nanoparticles changing with time, and the nucleation and growth rates were further calculated from the SAXS data. By changing solvents with the same functions of ligands but of different coordinating abilities, a correlation between the kinetics and thermodynamics was observed. The nucleation rate increases with the metal precursor reactivity, which corresponds to stronger solvent binding to the precursor. On the other hand, the stronger ligand-nanoparticle binding slows down the growth by lowering the surface capping density. To go deeper into the ligand-metal binding and kinetics correlation, the binding properties were tuned by changing other synthesis conditions, i.e., different temperatures and ligand to metal ratios (ligand concentration), and a qualitative discussion was given on the effects of these conditions on the synthesis kinetics and final particle size.
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Enhancing the Photo-electrode Features to Improve the Solar Conversion Efficiency in the Dye-Sensitized Solar CellNateq, Mohammad Hosein 29 October 2019 (has links)
Mesoporous semiconductors such as TiO2 nanoparticles, as well as transparent conducting oxides (TCOs) such as indium tin oxide films are typically employed for setting up the photo-electrode module in variety of photoelectrochemical cells including Dye-Sensitized Solar Cells (DSSCs). In order to exhibit a high performance efficiency, the photo-electrodes in such applications are required to be able to harvest the light and transport the generated electrons effectively. Accordingly mesoporous layers with high values of surface area and well-established pore structure along with highly transparent and conductive TCOs are deposited on suitable substrates through the physical or chemical vapor deposition methods. The processing facilities and materials required to fabricate such high-quality devices with high values of efficiency are complicated and expensive, whereas devices of lower quality do not fulfill the demands. This issue is of particular importance regarding the energy production and developing the solar cell technologies, as it is considered by the concept of “cost per watt”. Thus, a great deal of effort is being carried out globally to enhance the efficiency of affordably-produced solar cells such as low-cost DSSCs. Utilizing the wet chemical techniques such as sol-gel method which provide a considerably more affordable route to synthesize nanoparticles and deposit thin films without the need of applying high temperature or vacuum condition is a widely-used approach to decrease the processing expenses. However, to achieve an acceptable cost-per-watt ratio requires enhancing the obtained efficiency value as well, and therefore, modifying the processing procedures to improve the required features of the products are highly encouraged. This thesis focuses on two individual activities: synthesis of TiO2 nanoparticles, and also thin film deposition of a promising TCO called aluminum-doped zinc oxide (AZO); both obtained through the sol-gel route that is modified to contribute to nanostructures with suitable features for application in photoelectrochemical devices such as DSSC. In the first part, mesoporous anatase nanoparticles were synthesized through the surfactant-mediated sol–gel route. Through changing the refluxing time and water-to-surfactant molar ratio, as-prepared nanocrystals of high density and large and narrowly-distributed pore sizes were obtained, displaying surface area values up to 240 m2·g-1, much higher than the reported values for commercial TiO2-based catalysts. In the second part, sol–gel dip–coating of ZnO thin films doped with 2 at.% of aluminium ions was carried out. By altering the hydrolysis reaction and changing the thermal treatment procedure, thin films of highly c-axis preferred orientation were obtained with optical transmittance of around 80% and resistivity values down to 6 – 15 mΩ·cm, corresponding to sheet resistance of around Rsh ~ 500 Ω/sq. The obtained conductivity values, even though one order magnitude lower than those reported for the AZO thin film prepared via expensive techniques, are in the suitable range to improve the cost per watt ratio in applications such as inkjet printing of low-cost printed electronics and more affordable DSSC devices.
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Synthesis and Characterization of Reactive Core-Shell NanoparticlesSchwarb, Ryan Evan 11 May 2012 (has links)
No description available.
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From Single Colloidal Particles to Coupled Plasmonic SystemsMayer, Martin 07 December 2019 (has links)
By down-sizing noble metals to the nanoscale, striking new optical properties arise—investigated in the scientific field of plasmonics. The steady rise of developments, innovations, and interest in plasmonics is directly linked with the much broader field of (colloidal) nanotechnology and its breakthroughs. In order to harvest the full potential of colloidal plasmonics, optimizing the synthesis of colloidal nanoparticles, controlling the subsequent assembly of them into complex architectures, and fully understanding the emerging plasmonic properties is inevitable. Wet-chemical seed-mediated growth of colloidal building blocks and colloidal self-assembly offer the tool-sets to tackle the challenges of plasmonic applications.
Due to the intrinsic properties of colloids and the resulting (coupled) assemblies, distinct differences are evident in comparison to top-down fabrication based plasmonics. Among these properties, this thesis focuses on the true three-dimensionality of colloids—in vast contrast, top-down processes always rely on stacking of layered architectures. Strong plasmonic coupling interactions are predominantly defined by the inter-particle distances and the geometry of the cross section area by which adjacent particles interact. Consequently, unique plasmonic features emerge from the three-dimensional structure of colloids and the possibility to tune the dielectric environment by surface functionalization.
The objective of this work is to investigate and understand the plasmonics of coupled colloidal systems. Following this scope, the first part of this thesis introduces a new synthetic concept, which thereby aims to provide colloidal building blocks for plasmonic assemblies. The optical quality and spectral range can be boosted by applying silver nanoparticles instead of gold as plasmonic material. Herein, a general synthetic concept is introduced resulting in monodispersed and shape-pure silver nanoparticles in a highly controlled manner. By transferring the concept of living polymerization reactions to nanoparticle growth, secondary nucleation is successfully suppressed and the particle dimensions are freely tunable. Finally, chemical stability toward oxidation and functionalization reactions is obtained by covering silver particles with a sub-skin depth gold shell.
The second part summarizes the plasmonic properties arising from coupled particle assemblies fabricated by colloidal self-assembly. Therefore, the complexity of the coupled systems was systematically increased to observe the transition from local to collective coupling interactions. Starting from metallic film-coupled gold nanorods, the presence of a highly sensitive magnetic mode and its impact on the magnetic permeability were investigated. Next, the transition from local to collective coupling was observed by stepwise increase of the number of particles in a linear gold nanoparticle chain revealing the formation of a plasmon band in quasi-infinite particle chains.
Consequently, this work aims to advance the field of colloidal metasurfaces by optimizing the building blocks and by further comprehending the plasmonic coupling effects in colloidal assemblies. / Durch das Herunterskalieren von (Edel-)Metallen in den Nanometerbereich entstehen neue optische Eigenschaften, die im Wissenschaftsfeld der Plasmonik untersucht werden. Die stetige Weiterentwicklung, Innovation, und das steigende Interesse an der Plasmonik ist direkt mit dem weiter gefassten Gebiet der (kolloidalen) Nanotechnologie verbunden. Um das Potenzial der kolloidalen Plasmonik voll ausschöpfen zu können, ist es unumgänglich, die Synthese kolloidaler Nanopartikel zu optimieren, deren anschließende Anordnung zu komplexen Architekturen gezielt zu steuern, und die entstehenden plasmonischen Effekte vollständig zu verstehen. Das nasschemische Keim-vermittelte Wachstum kolloidaler Bausteine und die kolloidale Selbstanordnung bieten die geeigneten Werkzeuge für plasmonische Anwendungen. Aufgrund der intrinsischen Eigenschaften kolloidaler Partikel und den daraus resultierenden optischen Eigenschaften ihrer Anordnungen, ergeben sich deutliche Unterschiede zur Plasmonik von Top-down Systemen. Im Gegensatz zu diesen Systemen, die immer aus geschichteten Architekturen bestehen, handelt es sich bei kolloidalen Systemen um echte dreidimensionale Objekte. Starke plasmonische Kopplungswechselwirkungen werden hauptsächlich durch die Abstände zwischen Partikeln und die Geometrie des Querschnitts definiert, über die benachbarte Partikel interagieren. Folglich ergeben sich aus der dreidimensionalen Struktur von kolloidalen Nanopartikeln und der Möglichkeit, diese mit verschiedenen dielektrischen Umgebung zu funktionalisieren, einzigartige plasmonische Effekte.
Das übergeordnete Ziel dieser Arbeit besteht darin, die plasmonischen Effekte gekoppelter kolloidaler Systeme zu untersuchen und besser zu verstehen. Diesem Ziel folgend, wird im ersten Teil der Arbeit ein neues Synthesekonzept vorgestellt, das darauf abzielt geeignete kolloidale Bausteine für plasmonische Anordnungen zur Verfügung zu stellen. Verglichen mit Gold als Bausteinmaterial kann die optische Qualität und der Spektralbereich durch Nutzung der überlegenen plasmonischen Eigenschaften von Silbernanopartikeln gesteigert werden. Hier wurde ein allgemeines Synthesekonzept entwickelt, das auf kontrollierte Weise zu monodispersen und formreinen Silbernanopartikeln führt. Durch die Übertragung des Konzepts lebender Polymerisationsreaktionen auf das Nanopartikelwachstum, werden Nebenreaktionen (z.B. sekundäre Keimbildung) erfolgreich unterdrückt und die Partikelgröße wird dadurch genau einstellbar. Schließlich wurde durch die Überwachsung der Silberpartikel mit einer Goldschale unterhalb der Leitschichtdicke chemische Stabilität gegenüber Oxidations- und Funktionalisierungsreaktionen erhalten.
Im zweiten Teil werden die plasmonischen Eigenschaften gekoppelter Partikelanordnungen untersucht. Dafür wurde die Komplexität der gekoppelten Systeme systematisch erhöht, um den Übergang von lokalen zu kollektiven Kopplungsinteraktionen zu beobachten. Ausgehend von Goldstäbchen, die mit einem Metallfilm gekoppelt sind, wurde eine hochempfindliche magnetische Mode nachgewiesen und deren Einfluss auf die magnetische Permeabilität untersucht. Desweiteren wurde der direkte Übergang von lokaler zu kollektiver Kopplung durch schrittweise Erhöhung der Anzahl der Partikel in einer linearen Goldnanopartikelkette beobachtet, was zur Bildung eines Plasmonenbandes für quasi-unendlich lange Partikelketten führt.
Letztendlich ist das Ziel dieser Arbeit, kolloidale Metaoberflächen durch Optimierung der Bausteine und durch besseres Verständnis der plasmonischen Kopplungseffekte voranzubringen.
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