The overall performance of a material can be dramatically improved by tailoring its surface at the molecular level. The aim of this project was to develop a universal technique for attaching dendrimers (well-defined, nanoscale, functional polymers) and Jeffamines® (high molecular weight polymer chains) to the surface of any shaped solid substrate. This desire for controlled functionalization is ultimately driven by the need to improve material compatability in various biomedical applications. Atomic force microscopy (AFM) was used initially to study the packing and structure of Langmuir-Blodgett films on surfaces, and subsequently resulted in the first visualization of individual, spherically shaped, nanoscopic polyamidoamine dendrimers. The next goal was to develop a methodology for attaching such macromolecules to inert surfaces. Thin copolymer films were deposited onto solid substrates to produce materials with a fixed concentration of surface anhydride groups. Vapor-phase functionalization reactions were then carried out with trifluorinated amines to confirm the viability of this technique to bond molecules to surfaces. Finally, pulsed plasma polymerization of maleic anhydride took this approach one stage further, by forming well-adhered polymer films containing a predetermined concentration of reactive anhydride groups. Subsequent functionalization reactions led to the secure attachment of dendrimers and Jeffamines® at any desired packing density. An alternative route to biocompatibilization used 1,2-ethanedithiol to yield thiolated surfaces containing very high polymeric sulfur: carbon ratios.

No description available.

[pt] Nesta tese estudamos as propriedades de transporte de estruturas de pontos quânticos (PQs) ligados a contatos metálicos (CM). Descrevemos o formalismo dos bósons escravos através de sua aplicação ao sistema de um PQ ligado a um CM. Estudamos a nuvem Kondo (NK) dentro deste CM e desenvolvemos uma metodologia para calcular sua extensão (csi). Mostramos que (csi) é inversamente proporcional a temperatura Kondo TK. Aplicamos o método ao sistema de dois PQs. Estudamos o Regime Kondo (RK) molecular de um elétron (1e), a concorrência entre o antiferromagnetismo e o RK de dois elétrons (2e), a constituição da NK dentro dos CM e o valor de Tk. Calculamos a extensão da NK e a TK para diferentes valores da conexão entre os PQs e comparamos com os resultados obtidos a temperatura finita (TF). Mostramos a diminuição da NK quando TK e a conexão entre os PQs aumentam. Obtivemos um comportamento exponencial para TK em função desta conexão. Estudamos o sistema de dois PQs interagentes que se enxergam através de um terceiro PQ não interagente. Obtivemos a coexistência entre o RK e a correlação ferro (CF) para o sistema com 2e. À TF obtivemos um comportamento parabólico para a TK em função da conexão com o sítio do meio. Estes resultados diferem dos obtidos para o sistema de dois PQs conectados diretamente entre si. Estudamos uma molécula de três PQs interagentes conectados a dois CM através do PQ do meio e identificamos o estabelecimento de um regime Kondo dois estágios. Observamos uma CF quando o PQ do meio está ocupado e uma correlação antiferro CAF quando está vazio. Esta propriedade permite o funcionamento deste sistema como uma porta quântica. Mostramos que a leitura da informação desta porta pode ser mediada pelo RK. / [en] In this thesis we study the transport properties of quantum dot structures (QD s) connected to metallic leads (ML).We describe the slave boson mean field approach through it s application to a system of one QD connected to a (ML). We study the Kondo cloud (KC) inside this ML and develop a method to calculate it s extension (csi). We prove that ξ is proportional to the inverse of Kondo temperature TK. We apply the method to the system of two QD s and study the molecular KR for the system with one electron (1e), the competition between the antiferromagnetism and the KR for the system with an occupations of two electrons (2e), the formation of the Kondo cloud inside the ML and the TK value. We calculate the extension (csi) and TK for diferent values of the connection between the QD s and compare with the results found to finite temperature (FT).We show the decrease of the KC when TK and the connection between the dots increases. We obtain an exponential behavior of TK as a function of this connection. We study the system of two QD s with Coulomb interaction U correlated though a non interacting QD. We obtain the coexistence between the KR and the ferromagnetic correlation (FC) for the system with 2e. In a regime of finete temperature we obtain a parabolic behavior to the TK as a function of the connection with the central QD. This results are different of that obtained for the system of two QD s directly connected to each other. We study the molecule of three interacting QD s connected to two ML through the central one and identify a two stage Kondo effect. We observe a FC when the central QD is charged with one electron and an anti-ferromagnetic correlation (AFC) when this PQ is empty(or occupied if an even number of electrons). This properties permits the operation of this system as a quantum gate device. We prove that the reading of the information of this gate can be mediated through the KR.

[pt] Investigamos as propriedades de transporte de spin polarizado através de um ponto quântico conectado a dois terminais. A corrente elétrica que circula em nosso sistema pode ter sua polarização modulada através de um potencial de porta que controla o acoplamento spin-órbita (efeito Rashba). Nós estudamos o efeito de polarização do spin em um transistor constituído por um ponto quântico em que suas energias podem ser controladas através de um outro potencial de porta que opera apenas na região de confinamento. O alto grau de confinamento e correlação entre as cargas dão origem a fenômenos físicos interessantes que descreveremos neste trabalho. Nós demonstramos que através da manipulação de um potencial externo é possível controlar de uma maneira extremamente eficiente a intensidade e a polarização da corrente através do sistema. Outro parâmetro importante que iremos manipular para uma compreensão detalhada do sistema é o campo elétrico externo. Na segunda parte deste trabalho estudamos a evolução temporal da função de onda, suposta inicialmente como um pacote de onda circulando nosso sistema composto por um ponto quântico. Podemos comprovar efeitos de tunelamento ressonante e efeitos de interferência de nosso pacote inicial ao longo do tempo e, além disso, estudamos também efeitos de interação spin- órbita na polarização de nosso pacote de onda. / [en] We investigated spin polarized transport properties through a quantum dot connected with two terminals. An electric current that circulates in our system can have its polarization modulated with an external potential that controls the spin orbit coupling (Rashba effect). We studied the effect of spin polarization n a transistor constituted by a quantum dot where its energies can be controlled with a gate potential that operates only in the confinement region. The high confinement and correlation between the charges give rises to interesting phenomena that we describe in this work. We demonstrate that tuning an external potential it is possible to control with a extremely efficient precision the intensity and the polarization of the current through this system. Another important parameter that we used to better understand this system was the external electric field. In the second part of this work, we studied the time evolution of a wave function supposed to be initially a wave package circulating our system composed by a quantum dot. We can prove resonant tunneling effects and interference effects in such a wave package as time goes by and we also studied spin orbit interaction effects on the polarization of the carrier.

Die Diplomarbeit mit dem Thema: 'Konzeption und Herstellung von Systemdemonstratoren für miniaturisierte Im-Ohr-Lautsprecher mit drahtlosen Kommunikationsschnittstellen' konzentriert sich auf die Auslegung einer Schaltung eines neuartigen Lautsprechers, welche auf dem Prinzip der NED-Aktoren ('Nanoskaliger elektrostatischer Antrieb') arbeiten. Des Weiteren werden Gehäuse für die Im-Ohr-Anwendung als auch die Freifeldanwendung entwickelt.:Symbolverzeichnis Abkürzungsverzeichnis 1 Einleitung 2 Stand der Technik 2.1 Im-Ohr-Lautsprecher 2.2 Drahtlose Kommunikation 2.3 Kommerzielle Piezotreiber 3 Anforderungen an den Systemdemonstrator 4 Chipaufnahme 4.1 Anforderung 4.2 Konzeption und Umsetzung 5 Drahtlose Kommunikation 5.1 Anforderung 5.2 Konzept 5.3 Umsetzung 6 Verstärker 6.1 Anforderung 6.2 Konzeption und Umsetzung 6.2.1 Validierung des DRV2700 6.2.2 Thermisches Management der Verstärkerschaltung 6.3 Modellierung des Gehäuses für die Elektronik 7 Im-Ohr-Demonstrator 7.1 Anforderung 7.2 Konzeption und Umsetzung 8 Horn-Demonstrator 8.1 Anforderung 8.2 Konzeption und Umsetzung 9 Ergebnisse 9.1 Chipaufnahme 9.2 Verstärker 9.3 Gehäuse für Elektronik 9.4 Im-Ohr-Lautsprecher 9.5 Akustisches Horn 10 Realisierung mittels Entwicklungsplatine 11 Diskussion und Ausblick 12 Zusammenfassung Literatur Selbstständigkeitserklärung Anhang

[pt] Esta tese investiga as propriedades eletrônicas de sistemas nanoscópicos com interações de muitos corpos, dando origem ao efeito Kondo. Primeiramente estudamos a transição SU(4)-SU(2) devido a um campo magnético externo e as propriedades de filtro de spin de um nanossistema de dois pontos quânticos capacitivamente acoplados. A transição é caracterizada pela diferença entre as polarizações de spin da ocupação eletrônica nos dois pontos quânticos, como uma função do potencial de porta aplicado sobre os pontos quânticos. Apesar do fato de que o campo magnético externo quebra a simetria SU(4) do Hamiltoniano, o estado fundamental a preserva, como uma propriedade emergente, na região do espaço de parâmetros onde os elétrons não estão polarizados. As propriedades de filtro de spin devido à população eletrônica spin polarizada nos pontos quânticos também é discutida. Estas propriedades são estudadas usando o formalismo dos operadores de projeção, que descreve de forma muito acurada a física associada ao estado fundamental dos sistemas Kondo. No capítulo subsequente, analisamos os efeitos da interação spin-órbita num ponto quântico conectado a contatos, representados pelo modelo da impureza de Anderson no efeito Kondo. Contrariamente ao resultado prévio de vários outros autores, nós mostramos que a interação spin-órbita reduz exponencialmente a temperatura Kondo enquanto a ação da interação no próprio ponto quântico pode ser um mecanismo de destruição do regime Kondo, conforme quebra a simetria SU(2). Usando o modelo de Anderson com acoplamento spin-órbita nós propomos um transistor de spin feito de um ponto quântico conectado a uma nanofaixa submetida à interação spin-órbita Rashba, depositada sobre um substrato ferromagnético. O ponto quântico também é conectado a dois contatos metálicos laterais, através do qual a corrente flui ao longo do sistema. A interação spin-órbita Rashba cria um mecanismo de inversão do spin no ponto quântico. Nós mostramos que o sistema é capaz de operar como um transistor de spin. / [en] This thesis investigates the electronic properties of nanoscopic systems under the presence of many body interactions, given rise to the Kondo effect. Firstly we studied the SU(4)-SU(2) crossover driven by an external magnetic field and the spin-filter properties of a capacitively coupled double quantum dot nanosystem. The crossover is characterized by the difference between the spin polarization of the electronic occupation at the double quantum dot, as a function of the gate potential applied to the quantum dots. Despite the fact that the external magnetic field breaks the SU(4) symmetry of the Hamiltonian, the ground state preserves it, as an emergent property, in a region in the parameter space where the electron are not polarized. The spinfilter properties due the spin polarized electronic population at the dots is also discussed. These properties are studied using the projector projection operator approach, which describes very accurately the physics associated to the ground state of Kondo systems. In a subsequent chapter, we analyze the effect of the spin-orbit interaction in a quantum dot connected to leads, represented by the Anderson impurity model on the Kondo effect. Contrary to several other authors previous results, we show that the Rashba spin-orbit interaction exponentially reduces the Kondo temperature while the action of the interaction on the quantum dot itself could be a mechanism of destroying the Kondo regime, as it breaks SU(2) symmetry. Using the Anderson model with spin-orbit coupling we propose a spin transistor device made of a quantum dot connected to a Rashba spinorbit interacting nanoribbon, deposited on a ferromagnetic substrate. The quantum dot is also connected to two lateral metallic contacts, through which the current flows along the system. The Rashba spin-orbit interaction creates a spin-flip mechanism at the quantum dot. We show that the system is capable of operating as a spin-transistor.

Biological systems construct varieties of self-assembled architectures with incredible elegance and precession utilizing proteins as subunits to accomplish widespread functions. Inspired by natural systems, construction of artificial model systems with such sophistication and delicacy has become an intriguing field of research over the last two decades using so-called self-assembly process. Judiciously selected complementary building units encoded with specific chemical and structural information can be self-assembled into pre-programmed abiological architectures in a manner similar to biological self-assembly. In this regard, kinetically labile metal-ligand coordination has become an efficient and powerful protocol for the construction of highly intricate structures with specific topology and functionality due to its simple design principle, high bond enthalpy, and predictable directionality. Two-component self-assembly is very widely used methodology and easy to monitor. Recently, multi-component self-assembly has come up as an alternative and effective pathway to achieve complex architectures connecting more than two components in a single step. However, formation of selective single product from multicomponents is entropically unfavorable. Only a very few 3D architectures have been known, that are obtained from a mixture of ditopic and tri- or tetratopic donors with metal acceptors with or without employing templates. Development of template-free multicomponent architectures is still in its infancy. Strong tendency of Pd(II)/Pt(II) to attain square-planar geometry around the metal center and kinetically labile nature of Pd(II)/Pd(II)-N(pyridine) bonds made them chemists’ favourite to engineer desired supramolecular coordination architectures with structural resemblance to Platonic or Archimedean solids by employing symmetrical pyridyl donors due to their predictable directionality. In case of poly-imidazole donors, free rotation of C-N bond connecting imidazole and phenyl ring allows various dispositions of the donating nitrogen with respect to the aromatic backbone, and therefore, the structural topology of the architectures, made of poly-imidazole ligands becomes much more interesting as compared to symmetrical Platonic or Archimedean solids. The physico-chemical properties of self-assembled coordination cages depend on the structures of the complexes. Presence of large internal cavity surrounded by aromatic core, provides an excellent environment for the encapsulation of varieties of guest molecule or as nano-reactors for different organic transformations. Structural investigation in terms of packing interactions, solvent molecules, intermolecular channels can sometimes determine the property of such self-assembled materials as well. Presence of acidic water as well as H-bonded 3D-networks of water molecules in molecular pockets make them potential material for proton conduction. In addition, metal-ligand coordination offers opportunity to introduce new functionality through pre-synthetic modification of the building constituents to influence the property of the supramolecular systems. Incorporation of unsaturated ethynyl functionality attached to the heavy transition metal is expected to exhibit efficient luminescence due to the facile metal to ligand charge transfer (MLCT). Hence, the final assemblies can be employed as chemosensors for electron-deficient nitroaromatics, which are the chemical signature of many of the commercially available explosives. The present investigation is focused on design and construction of discrete, nanoscopic coordination cages with unusual structural topology employing mainly imidazole-based donors with Pd(II)/Pt(II) acceptors and their applications in catalysis, chemosensing, and proton conduction. CHAPTER 1 of the thesis provides a general introduction to self-assembly focusing on the importance and advantages of metal-ligand directional bonding approach towards the construction of supramolecular architectures with various structural topologies. This chapter also includes a brief review on the applications of such coordination cages in various fields especially as ‘molecular flask’ for the observation of unique chemical phenomena and unusual reactions. Part A of CHAPTER 2 describes the synthesis of a new hollow Pd6 water soluble cage [{(tmen)Pd}6(timb)4](NO3)12 (1) via two-component self-assembly of a triimidazole donor and 90° Pd(II) acceptor [tmen = N,N,N’,N’-tetramethylethylenediamine, timb = 1,3,5-tris(1-imidazolyl)benzene]. The assembly was successfully crystallized with a hydrophilic dianionic benzoquinone derivative (formed in situ by the decomposition of DDQ) as [{(tmen)Pd}6(timb)4](NO3)10()2(H2O)18 (3), and a hydrophobic sterically demanding aromatic aldehyde as [{(tmen)Pd}6(timb)4](NO3)12{()4a}2(H2O)27 (5a) [where 2H2 = 2,3-dichloro-5,6-dihydroxycyclohexa-2,5diene-1,4-dione, 4a = 1-pyrenecarboxaldehyde,  = exohedral and  = endohedral] to confirm the hydrophobic nature of the cavity. Experiments were carried out to show that the hydrophobic confined nanospace of the cage (1) catalyses the Knoevenagel condensation of a series of different aromatic monoaldehydes with active methylene compounds in ‘green’ aqueous medium. The Knoevenagel condensation reaction is basically a dehydration reaction because water is a by-product. So the presence of water should, in principle, promote the backward reaction as per Le Chatelier’s principle. In general, these reactions with organic substrates are not performed in water. However, difficulty has been overcome using hydrophobic cavity of the cage. It has also been established that the cavity of the cage also enhances the rate of Diels-Alder reaction of 9-hydroxymethylanthracene with N-phenylmaleimide/N-cyclohexylmaleimide. Figure 1. Catalytic Knoevenagel condensation and Diels-Alder reaction using hydrophobic cavity of the cage (1) in aqueous medium. Part B of CHAPTER 2 reports unique three-component self-assembly incorporating both tri- and tetra-topic donors. Until now, a very few 3D-architectures have been known that are obtained from self-assembly of ditopic and tri- or tetratopic donors with metal acceptors. Scheme 1. Three-component self-assembly of a Pd7 cage (1) from cis-blocked Pd(II) 90° acceptor (M), tri-imidazole (timb) and tetra-imidazole (tim) donors. Self-assembled multicomponent discrete architecture composed of both tri- and tetra-topic donors is yet to be reported due to difficulty in prediction of the final structure from the mixture of ligands having multiple donor sites. The first example of self-sorted Pd7 molecular boat [{(tmen)Pd}7(timb)2(tim)2](NO3)14(H2O)20 (1) [tmen = N,N,N’,N’-tetramethylethylenediamine, timb = 1,3,5-tris(1-imidazolyl)-benzene, tim = 1,2,4,5-tetrakis(1-imidazolyl)benzene] was synthesized via three-component self-assembly of cis-(tmen)Pd(NO3)2, tetra- (tim) and tri-topic donors (timb) in a 7:2:2 ratio. The cavity of this cage was also utilized as a nanoreactor for catalytic Knoevenagel condensations of a series of aromatic aldehydes with 1,3-dimethylbarbituric acid (e) and Meldrum’s acid (f) in aqueous media. CHAPTER 3 presents the results of an investigation on how simple variation of length and coordination mode of linear donors can self-discriminate into markedly different complex architectures, from Pd8 molecular swing [{(tmen)Pd}8(tim)2(bpy)4](NO3)16 (1) or [{(tmen)Pd}8(tim)2(stt)5](NO3)6 (2) to Pd6 molecular boat [{(tmen)Pd}6(tim)2(bpe/dpe/pin/dpb)2](NO3)12, (3/4/5/6). Also by enhancing denticity [bidentate to tridentate (ptp)] as well as introducing asymmetry, they self-sort into Pd7 molecular tent [{(tmen)Pd}7(tim)2(ptp)2](NO3)14 (7) by employing it in a self-assembly of cis-(tmen)Pd(NO3)2 and tetraimidazole (tim) donor [where tmen = N,N,N’,N’-tetramethylethylenediamine, bpy = 4,4’-bipyridyl, stt = sodium terephthalate, bpe = trans-1,2-bis(4-pyridyl)ethylene, dpe = 1,2-di(pyridin-4-yl)ethane, pin = N-(pyridin-4-yl)isonicotinamide, dpb = 1,4-di(pyridin-4-yl)benzene, ptp = 6'-(pyridin-4-yl)-3,4':2',4''-terpyridine, and tim = 1,2,4,5-tetrakis(1- imidazolyl)benzene]. In these cases, control of the geometrical principles and stereo-electronic preferences of the building units allowed the formation of such intricate architectures. Some of these assemblies represent first examples of such types of structures, and their formation would not be anticipated by taking into account only the geometry of the donor and acceptor building units. In addition to their direct structural confirmation using single crystal X-ray diffraction analysis, propensity of the assemblies (1 and 3) to form inclusion complexes with large guest like C60 in solution was also demonstrated by fluorescence quenching experiment. The high KSV values for both the assemblies 1 (1.0 × 10-5 M-1) and 2 (1.6 × 10-6 M-1) with C60 indicated the propensity of these assemblies to form complexes with C60 in solution. Furthermore, inspection of crystal packing of other five complexes (2 and 4 - 7) revealed the presence of water molecules H-bonded with NO3– (O-H···O=N) and 3D H-bonded networks of water in the intermolecular pockets. Interestingly, the present complexes (2 and 4 - 7) show high conductivity across low-humidity range at ambient temperature and achieve a conductivity of ~10-3 Scm-1 at 75% relative humidity and 296 K. These supra-molecular architectures represent a new generation of discrete materials that display high proton conductivity under ambient conditions with activation energy comparable to that of Nafion. Scheme 2. Exclusive formation of Pd8 molecular swings (1 and 2), Pd6 molecular boats (3-6), and Pd7 molecular tent (7) via self-sorting. CHAPTER 4 presents self-selection by synergistic effect of morphological information and coordination ability of the ligands through specific coordination interactional algorithms within dynamic supramolecular systems involving a tetratopic Pd(II) acceptor and three different pyridine- and imidazole-based donors (La - Lc) [La = 1,3-bis((E)-2-(pyridin-3-yl)vinyl)benzene, Lb = 1,3-di(1H-imidazol-1-yl)benzene, and Lc = tris(4-(1H-imidazol-1-yl)phenyl)amine]. Three different cages, ‘paddle wheel’ cluster Pd2(La)4(NO3)4 (2a), molecular barrel Pd3(Lb)6(NO3)6 (2b) and molecular sphere Pd6(Lc)8(NO3)12 (2c) were first synthesized via two-component self-assembly of a tetratopic Pd(II) acceptor (1) and individual pyridine- and imidazole-based donors (La - Lc). When all the four components were allowed to interact in a complex reaction mixture, only one out of three cages was isolated. The inherent dynamic nature of the kinetically labile coordination bond allows constitutional adaptation through component exchange in the competition experiment involving multiple constituents to self-organize into specific combination and thereby, achieve the thermodynamically most stable assembly. The preferential binding affinity towards a particular partner was also established by transforming a non-preferred cage to a preferred cage by the interaction with the appropriate ligand and thus, this represents the first examples of two-step cage-to-cage transformation through constitutional evolution of Figure 2. Cage-to-cage transformation from non-preferred cage to preferred cage upon treatment with appropriate ligand; and Nyquist plots of the complexes (2b and 2c) under 98% RH condition and ambient temparature. dynamic systems induced by both coordination ability and geometry of the ligand. Moreover, computational study further supported the fact that coordination interaction of imidazole moiety to Pd(II) is enthalpically more preferred compared to pyridine which drives the selection process. In addition, analysis of crystal packing of both the complexes (2b and 2c) indicated the presence of strong H-bonds between NO3- and water molecules; as well as H-bonded 3D-networks of water. Interestingly, both the complexes exhibit promising proton conductivity (10-5 to ca. 10-3 S cm-1) at ambient temperature under relative humidity of ~98% with low activation energy. CHAPTER 5 covers design and synthesis of new organometallic building block 1,3,5-tris(4-trans-Pt(PEt3)2I(ethynyl)phenyl)benzene (1) incorporating Pt-ethynyl functionality and [2 + 3] self-assembly of its nitrate analogue 1,3,5-tris(4-trans-Pt(PEt3)2(ONO2)(ethynyl)phenyl)benzene (2) with “clip” type bidentate donors (L1 – L3) separately afforded three trigonal prismatic architectures (3a – 3c), respectively (Scheme 3), Scheme 3. Schematic presentation of three different donors (L1 – L3) and a new planar tritopic acceptor (2) and their [3 + 2] self-assembly into trigonal prismatic architectures (3a - 3c). [L1 = N1,N3-di(pyridin-3-yl)isophthalamide; L2 = 1,3-bis((E)-2-(pyridin-3-yl)vinyl)benzene; L3 = 1,3-bis(pyridin-3-ylethynyl)benzene]. All these prisms were characterized and their shapes/sizes are predicted through geometry optimization employing molecular mechanics universal force field (MMUFF) simulation. The extended -conjugation including the presence of Pt-ethynyl functionality make them electron rich as well as luminescent in nature. As expected, cages 3b and 3c exhibit fluorescent quenching in solution upon addition of picric acid [PA], which is a common constituent of many explosives. Interestingly, the non-responsive nature of fluorescent intensity towards other electron-deficient nitro-aromatic explosives (NAEs) makes them promising selective sensors for PA with a detection limit deep down to ppb. Complexes 3b – c represent the first examples of molecular metallocages as selective sensors for picric acid. Furthermore, solid-state quenching of fluorescent intensity of the thin film of 3b upon exposure to saturated vapor of picric acid draws special attention for infield application.

Optical properties of nanoscopic materials have been intensively pursued over last couple of decades due to their tunable optical properties. Recent interests in this field have been mainly focused on the preparation of ordered arrays of nano materials and study of their optical properties. These interests have been motivated by the applications of such systems for nano photonic devices. Theoretical predictions from such systems reveal complex absorption and emission properties, different from individual ones mainly because of energy transfer between them. These properties can be controlled further by preparing hybrid arrays of nanostructures, including nano crystals of different types. Hybrid arrays with semiconductor quantum dots and metallic nanoparticles are an example of such system. Optical properties of such a system can be tuned by controlling the interaction between excitons and plasmons. This thesis presents the experimental studies on optical properties of polymer capped nanoparticles, quantum dot arrays and hybrid arrays with semi conducting quantum dot and metal nanoparticles. A brief summary of the experimental methods and results have been highlighted below. In this thesis, we study the controlling decay dynamics of CdSe quantum dots by 2D photonic-plasmonic and metamaterial templates. In Chapter 1 we provide a detailed background on the theoretical methods of Light-Matter interaction at nano scale. We also have given the detailed information on both weak and strong coupling region in the light-matter interaction. This chapter includes the discussion controlling light-matter interaction with both photonic crystals and plasmonic materials with some appropriate examples from the literature. In this chapter we have also explained the relevance of our work in this area and organization of the chapters and there importance has given. In chapter 2 we provide details about various experimental methods used in this thesis. A brief introduction is given on the materials used, their synthesis and the preparation of different type of self assembled plasmonic-photonic templates. This chapter starts with an explanation of the materials used along with the justification; moves on to the preparation of different 2D wire metamaterial. The characterization techniques for these different types of templates like spectroscopic ellipsometer, atomic force spectroscopy, scanning electron microscopy and transmission electron microscopy are discussed. We also discussed optical spectroscopic techniques like confocal optical microscopy and near field optical microscopy techniques. The first two chapters form the basis of all the experiments discussed in the forth coming chapters. In chapter 3 Finite difference time domain (FDTD) simulations were performed on two different plasmonic sub wavelength photonic templates embedded with CdSe quantum dots. Tunable loading of these templates with plasmonic nano antenna allowed control of the emission from the embedded quantum dots. We discuss how large loading of nano antenna can effectively control the optical density of states for the quantum dots leading to enhancement of their radiative decay rates as observed in experiments. On the other hand, at low level of loading, while FDTD fails to capture the observed enhancement of decay rates in experiment, an alternative mechanism is suggested to exist in such cases. Thus, subtle interplay of multiple mechanisms engineered by appropriate placement and loading of plasmonic nano antenna in such templates is demonstrated as an effective method to control optical density of states and hence spontaneous emission of embedded quantum dots. In Chapter 4 we report results of controlled tuning of the local density of states (LDOS) in versatile, flexible and hierarchical self assembled plasmonic templates. Using 5 nm diameter gold (Au) spherical nano antenna within a polymer template randomly dispersed with quantum dots, we show how the photo-luminescence intensity and lifetime anisotropy of these dots can be significantly enhanced through LDOS tuning. Finite difference time domain simulations corroborate the experimental observations and extend the regime of enhancement to a wider range of geometric and spectral parameters bringing out the versatility of these functional plasmonic templates. It is also demonstrated how the templates act as plasmonic resonators for effectively engineer giant enhancement of the scattering efficiency of these nano antenna embedded in the templates. Our work provides an alternative method to achieve spontaneous emission intensity and anisotropy enhancement with true nanoscale plasmon resonators. In chapter 5 we reported enhancement optical properties of quantum dot monolayers on top of the functional, flexible and hierarchical self-assembled plasmonic template using extremely small gold (Au) nanoparticles of diameter 5 nm. We reported how the LODS changes with different polarizations for CdSe quantum dot present on top of the template. We observed the enhanced radiative LDOS from the nano antenna filled pores indicating plasmonic enhanced emission from these templates. The difference in spectral and spatial profile of LDOS and Pur-cells with polarization of quantum dot emission results in the anisotropic emission in these templates. In chapter 6 we reported the emergence of strong coupling between quantum emitters and 2D hyperbolic metamaterials (HMM). We studied both spectral dependence and effect of filling fraction of the HMM on strong interaction. We also show the controlling of the transition from weak coupling region to strong coupling region by changing the distance between QD monolayer and HMM. By using FDTD simulation we are able to calculate both spectral function S(!) and coupling efficiency. In chapter 7 as a conclusion we concluded the work done in this thesis. We also indicated the future directions in this field and possible application.

In AP 1.4 wurde ein Verfahren zur Schaltzeitprognose verkehrsabhängiger Lichtsignalanlagen entwickelt, welches auf eine Vielzahl weiterer Lichtsignalanlagen anwendbar ist. Weiterhin wurden (AP.1.4.5) im Bereich der spurgenauen Ortung, die auf Basis von GPS ermittelten Positionen durch Fusion mit anderen Sensordaten, wie der axialen Beschleunigungen und den Drehraten um die Fahrzeughochachse sowie der Einbeziehung einer digitalen Karte (Digital Enhanced Map), diese hinsichtlich einer Spurdetektion weiterhin verbessert. Im Bereich der Datenübertragung (LSA-Fzg.) konnte die erste Teilstrecke von der Verkehrsmanagementzentrale zum Serviceprovider im Labor untersucht werden. In AP 2.1 wurde eine auf der optimalen Steuerung basierte Methode zum Energiemanagement von seriellen Hybriden entwickelt. Die optimale Ansteuerung von Motor-Start-Stopp, Gangwahl und Momentenaufteilung wird modellprädiktiv unter Beachtung des Kraftstoffverbrauchs und der Schademissionen berechnet. Nach Anpassung auf praktische Randbedingungen, lässt sich diese Methode in zukünftigen Hybridfahrzeugen als optimales Energiemanagement nutzen. Die in AP 3.1 entwickelte Softwareumgebung zur gekoppelten Fahrzeug und Verkehrssimulation wurde an Beispielszenarien getestet. Für ein Modell der Versuchsstrecke wurde umfangreiche Analysen des Ampelassistenzfunktion in komplexen Verkehrsszenarien durchgeführt. Für eine Variation verschiedener Parameter, wie Wirkreichweite, Verkehrsstärke, usw. konnten Aussagen über das Potential getroffen werden. In Zusammenarbeit mit AP 3.3 wurde ein Ampelassistenzsystem und die Ansteuerung des Active-Force-Feedback Pedals im Demonstrator implementiert. In AP 3.3 wurde ein Konzept zur Darstellung von LSA-Daten im Fahrzeug erarbeitet. Dieses wurde in einem Versuchsträger umgesetzt. Dazu wurde der Versuchsträger hardwareseitig ertüchtigt, und für die Untersuchung verschiedener Varianten der Darstellung eingesetzt.

In AP 1.4 wurde ein Verfahren zur Schaltzeitprognose verkehrsabhängiger Lichtsignalanlagen entwickelt, welches auf eine Vielzahl weiterer Lichtsignalanlagen anwendbar ist. Weiterhin wurden (AP.1.4.5) im Bereich der spurgenauen Ortung, die auf Basis von GPS ermittelten Positionen durch Fusion mit anderen Sensordaten, wie der axialen Beschleunigungen und den Drehraten um die Fahrzeughochachse sowie der Einbeziehung einer digitalen Karte (Digital Enhanced Map), diese hinsichtlich einer Spurdetektion weiterhin verbessert. Im Bereich der Datenübertragung (LSA-Fzg.) konnte die erste Teilstrecke von der Verkehrsmanagementzentrale zum Serviceprovider im Labor untersucht werden. In AP 2.1 wurde eine auf der optimalen Steuerung basierte Methode zum Energiemanagement von seriellen Hybriden entwickelt. Die optimale Ansteuerung von Motor-Start-Stopp, Gangwahl und Momentenaufteilung wird modellprädiktiv unter Beachtung des Kraftstoffverbrauchs und der Schademissionen berechnet. Nach Anpassung auf praktische Randbedingungen, lässt sich diese Methode in zukünftigen Hybridfahrzeugen als optimales Energiemanagement nutzen. Die in AP 3.1 entwickelte Softwareumgebung zur gekoppelten Fahrzeug und Verkehrssimulation wurde an Beispielszenarien getestet. Für ein Modell der Versuchsstrecke wurde umfangreiche Analysen des Ampelassistenzfunktion in komplexen Verkehrsszenarien durchgeführt. Für eine Variation verschiedener Parameter, wie Wirkreichweite, Verkehrsstärke, usw. konnten Aussagen über das Potential getroffen werden. In Zusammenarbeit mit AP 3.3 wurde ein Ampelassistenzsystem und die Ansteuerung des Active-Force-Feedback Pedals im Demonstrator implementiert. In AP 3.3 wurde ein Konzept zur Darstellung von LSA-Daten im Fahrzeug erarbeitet. Dieses wurde in einem Versuchsträger umgesetzt. Dazu wurde der Versuchsträger hardwareseitig ertüchtigt, und für die Untersuchung verschiedener Varianten der Darstellung eingesetzt.:I. Versionsübersicht 4 II. Kurze Darstellung 5 1. Aufgabenstellung 5 2. Voraussetzungen 6 3. Planung und Ablauf des Vorhabens 7 4. Wissenschaftlicher und technischer Stand 8 5. Bekannte Konstruktionen, Verfahren und Schutzrechte 9 6. verwendete Fachliteratur und Informations- und Dokumentationsdienste 9 7. Zusammenarbeit mit anderen Stellen 10 III. Eingehende Darstellung 11 1. Arbeitsinhalte und erzielte Ergebnisse 11 AP 1.4: Datenmanagement 11 AP 2.1: Range-Extender-Betriebsstrategien 40 AP 3.1: Fahrstrategie 63 AP 3.3: Mensch-Maschine-Interface 73 2. Nutzen der Ergebnisse 81 3. Fortschritt bei anderen Stellen 82 4. Veröffentlichungen und studentische Arbeiten 83 Vorträge 83 Publikationen 83 Studentische Arbeiten 84 IV. Literaturverzeichnis 86