This thesis examines the feasibility of using conventional semiconductors, specifically GaAs, as a plasmonic material at the operating wavelength of 1550nm, due to its many merits such as achievable low losses and mature micro-fabrication technologies. A theoretical study is performed on GaAs that yielded the condition for plasmonic behaviour at a minimum free carrier density of 7.2 x 10^20cm^-3 in bulk materials. The most feasible route to achieving this condition is determined to be intense optical excitation, and the required intensity considering a 150fs pulse at the above bandgap wavelength of 870nm is approximately 2.55TW/cm^2. A Bragg reflection ridge waveguide (BRW) using GaAs-AlGaAs is designed and micro-fabricated, and a counter-propagating pump-probe experiment is devised to test the plasmonic effect using the BRW. Results from two different ultrafast lasers include the observation of pump (870nm and 800nm) coupling to fundamental Bragg modes, and the measurement of the pump transmission spectrum.

<p>The electromagnetic properties of various plasmonic nanostructures are investigated. These nanostructures, which include random clusters, controlled clusters and particle-film hybrids are applied to surface-enhanced Raman scattering (SERS). A variety of techniques are utilized to fabricate, characterize, and model these SERS-active structures, including nanoparticle functionalization, thin film deposition, extinction spectroscopy, elastic scattering spectroscopy, Raman scattering spectroscopy, single-assembly scattering spectroscopy, transmission electron microscopy, generalized Mie theory, and finite element method. </p><p>Initially, the generalized Mie theory is applied to calculate the near-field of the small random clusters to explain their SERS signal distribution. The nonlinear trend of SERS intensity versus size of clusters is demonstrated in experiments and near-field simulations. </p><p>Subsequently, controlled nanoparticle clusters are fabricated for quantitative SERS. A 50 nm gold nanoparticle and 20nm gold nanoparticles are tethered to form several hot spots between them. The SERS signal from this assembly is compared with SERS signals from single particles and the relative intensities are found to be consistent with intensity ratios predicted by near-field calculation.</p><p>Finally, the nanoparticle/film hybrid structure is studied. The scattering properties and SERS activity are observed from gold nanoparticles on different substrates. The gold nanoparticle on gold film demonstrates high field enhancement. Raman blinking is observed and implies a single molecule signal. Furthermore, the doughnut shape of Raman images indicates that this hybrid structure serves as nano-antenna and modifies the direction of molecular emission. </p><p>In additional to the primary gap dipole utilized for SERS, high order modes supported by the nanoparticle/film hybrid also are investigated. In experiments, the HO mode show less symmetry compared to the gap dipole mode. The simulation indicates that the HO modes observed may be comprised of two gap modes. One is quadrupole-like and the other is dipole-like in terms of near-field profile. The analytical treatment of the coupled dipole is performed to mimic the imaging of the quadrupole radiation.</p> / Dissertation

Nowadays plasmonics is rapidly developing areas from fundamental studies to more application driven research. This dissertation contains three different research topics on plasmonics. In the first research topic, by modulating the zone width of a plasmonic zone plate, we demonstrate that a beam focused by a proposed plasmonic zone plate lens can be achieved with higher intensity and smaller spot size than the diffraction-limited conventional zone plate lens. This sub-diffraction focusing capability is attributed to extraordinary optical transmission, which is explained by the complex propagation constant in the zone regions afforded by higher refractive index dielectric layer and surface plasmons. On the other hand, the resulted diffraction efficiency of this device is relatively low. By introducing a metal/dielectric multilayered zone plate, we present higher field enhancement at the focal point. This higher field enhancement originates not only from surface plasmon polaritons-assisted diffraction process along the propagation direction of the incident light (longitude mode), but also from multiple scattering and coupling of surface plasmons along the metal/dielectric interface (transverse mode). In the second research topic, we suggest a novel concept of SERS-active substrate applications. The surface-enhanced Raman scattering enhancement factor supported by gap surface plasmon polaritons is introduced. Due to higher effective refractive index induced by gap surface plasmon polaritons in the spacer region between two metal plates, incident light tends to localize itself mostly in the medium with higher refractive index than its adjacent ones and thereby the lights can confine with larger field enhancement. In the last research topic, we offer a simple structure in which a gold dipole antenna is formed on the SiC substrate. Surface phonon polaritons, counterparts of surface plasmon polaritons in the mid-infrared frequencies, are developed. Due to the synergistic action between the conventional dipole antenna coupling and the resonant excitation of surface phonon polaritons, strong field enhancement in the gap region of dipole antenna is attained. Most of research topics above are expected to find promising applications such as maskless nanolithography, high resolution scanning optical microscopy, optical data storage, optical antenna, SERS-active substrate, bio-molecular sensing and highly sensitive photo-detectors.

In this study, optical behavior of metal nanoparticles having dimensions smaller than the wavelength of visible light is studied experimentally and numerically. Gold (Au) and silver (Ag) nanoparticles are studied due to their superior optical properties when compared to other metals. A compact code based on Discrete Dipole Approximation (DDA) is developed to compute extinction efficiencies of nanoparticles with various different properties such as material, dimension and geometry. To obtain self consistent nanoparticle arrays with well defined geometries and dimensions, Electron Beam Lithography (EBL) technique is mainly used as the manufacturing method. Dose parameters required to produce nanoparticles with dimensions down to 50 nm over substrates with different electrical conductivities are determined. Beam current is found to affect the doseV size relation. The use of thin Au films as antistatic layer for e-beam patterning over insulating substrates is considered and production steps, involving instabilities due to contaminants introduced to the system during additional removal steps, are clarified. 4 nm thick Au layer is found to provide sufficient conductivity for e-beam patterning over insulating substrates. An optical setup capable of performing transmittance and reflectance measurements of samples having small areas patterned with EBL is designed. Sizes of the metal nanoparticles are determined by scanning electron microscope (SEM) and spectral data obtained using the optical setup is analyzed to find out the parameters affecting the localized surface plasmon resonances (LSPR). Arrays of particles with diameters between 50 &ndash / 200 nm are produced and optically analyzed. Size and shape of the nanoparticles are found to affect the resonance behavior. Furthermore, lattice constants of the particle arrays and surrounding medium are also shown to influence the reflectance spectra. Axes with different lengths in ellipsoidal nanoparticles are observed to cause distinguishable resonance peaks when illuminated with polarized light. Peak intensities obtained from both polarizations are observed to decrease under unpolarized illumination. Binary systems consisting of nanosized particles and holes provided better contrast for transmitted light.

<p>All conducting polymers are potentially electrochromic, owing to the injection of charge carriers that changes their electronic structure and results in a shift of their optical absorption towards higher wavelengths. PEDOT-PSS and PEDOT-S are very promising materials in terms of electrochromic properties, due to the good contrast existing between their doped and undoped forms. However this contrast has to be enhanced in order to design more efficient electrochromic devices, and new solutions should thus be found in order to solve this issue.</p><p>Surface plasmons are described as electromagnetic waves propagating along the surface between a dielectric and a metal. Coupled to an incident radiation, they create an energy loss in the light transmitted and reflected by the interface. When the metallic surface is periodically corrugated, this absorption phenomenon due to plasmonic resonance occurs at a specific wavelength that depends on several parameters, such as the incidence angle, the dielectric constants of the two media and the grating period. By coating metallic gratings with electrochromic polymers, we may thus be able to trigger a plasmonic absorption at a given wavelength and shift it upon reduction or oxidation of the material.</p><p>Electrochromic devices consisting of PEDOT-PSS or PEDOT-S spin-deposited on gold and silver gratings were investigated by UV-visible reflectance measurements. The periodically corrugated structures were reproduced from commercial gratings by soft nanolithography and were analyzed by AFM. Some electrochromic cells exhibited new colors or a high shift of the plasmonic resonance upon redox switching of the polymer film. Depending on the step and the nature of the grating employed, this shift could reach 20 nm in the case of PEDOT-PSS and more than 100 nm for PEDOT-S. A theoretical model was found to predict the wavelength of plasmonic excitation and the orientation of the shift.</p>

In dieser Arbeit wurden sphärische Gold Nanopartikel (NP) mit einem Durchmesser größer ~ 2 nm, Gold Quantenpunkte (QDs) mit einem Durchmesser kleiner ~ 2 nm sowie Gold Nanostäbchen (NRs) unterschiedlicher Länge hergestellt und optisch charakterisiert. Zudem wurden zwei neue Synthesevarianten für die Herstellung thermosensitiver Gold QDs entwickelt werden. Sphärische Gold NP zeigen eine Plasmonenbande bei ~ 520 nm, die auf die kollektive Oszillation von Elektronen zurückzuführen ist. Gold NRs weisen aufgrund ihrer anisotropen Form zwei Plasmonenbanden auf, eine transversale Plasmonenbande bei ~ 520 nm und eine longitudinale Plasmonenbande, die vom Länge-zu-Durchmesser-Verhältnis der Gold NRs abhängig ist. Gold QDs besitzen keine Plasmonenbande, da ihre Elektronen Quantenbeschränkungen unterliegen. Gold QDs zeigen jedoch aufgrund diskreter Energieniveaus und einer Bandlücke Photolumineszenz (PL). Die synthetisierten Gold QDs besitzen eine Breitbandlumineszenz im Bereich von ~ 500-800 nm, wobei die Lumineszenz-eigenschaften (Emissionspeak, Quantenausbeute, Lebenszeiten) stark von den Herstellungs-bedingungen und den Oberflächenliganden abhängen. Die PL in Gold QDs ist ein sehr komplexes Phänomen und rührt vermutlich von Singulett- und Triplett-Zuständen her. Gold NRs und Gold QDs konnten in verschiedene Polymere wie bspw. Cellulosetriacetat eingearbeitet werden. Polymernanokomposite mit Gold NRs wurden erstmals unter definierten Bedingungen mechanisch gezogen, um Filme mit optisch anisotropen (richtungsabhängigen) Eigenschaften zu erhalten. Zudem wurde das Temperaturverhalten von Gold NRs und Gold QDs untersucht. Es konnte gezeigt werden, dass eine lokale Variation der Größe und Form von Gold NRs in Polymernanokompositen durch Temperaturerhöhung auf 225-250 °C erzielt werden kann. Es zeigte sich, dass die PL der Gold QDs stark temperaturabhängig ist, wodurch die PL QY der Proben beim Abkühlen (-7 °C) auf knapp 30 % verdoppelt und beim Erhitzen auf 70 °C nahezu vollständig gelöscht werden konnte. Es konnte demonstriert werden, dass die Länge der Alkylkette des Oberflächenliganden einen Einfluss auf die Temperaturstabilität der Gold QDs hat. Zudem wurden verschiedene neuartige und optisch anisotrope Sicherheitslabels mit Gold NRs sowie thermosensitive Sicherheitslabel mit Gold QDs entwickelt. Ebenso scheinen Gold NRs und QDs für die und die Optoelektronik (bspw. Datenspeicherung) und die Medizin (bspw. Krebsdiagnostik bzw. -therapie) von großem Interesse zu sein. / In this thesis, the synthesis and optical characterization of spherical gold nanoparticles (NP) with diameters larger than ~ 2 nm, gold quantum dots (QDs) with diameters smaller than ~ 2 nm and gold nanorods (NRs) with different lengths are presented. In addition, a novel one-pot synthesis for the preparation of thermosensitive gold QDs is introduced. Gold NP solutions appear red colored due to their strong absorption in the visible range at ~ 520 nm. This absorption band is a result of surface plasmon resonance, which is caused by the coherent oscillation of conduction band electrons induced by an electromagnetic field. In contrast to spherical gold NPs, gold NRs show two surface plasmon bands due to their anisotropic shape, a transverse plasmon band at ~ 520 nm and a longitudinal plasmon band depending on the aspect ratio (length-to-width-ratio) of the gold NRs. If the size of the gold NPs decreases to values below ~ 2 nm, quantum-size confinement occurs and the surface plasmon band disappears. Additionally, the overlap between conduction band and valence band disappears, discrete electronic levels arise and a band gap is created. As a consequence of quantum confinement, the gold QDs show photoluminescence (PL) upon UV-irradiation. The gold QDs synthesized via the one-pot synthesis exhibit a broadband luminescence between 500 nm and 800 nm. The luminescence properties (emission peak, quantum yield, lifetime) strongly depend on the synthetic parameters like reaction temperature, stoichiometry and the surface ligand. Gold NRs and gold QDs were incoroporated into different polymers (e.g. cellulose triacetate). Polymer nanocomposite films showing optical anisotropy are obtainded by stretching polymer films containing gold NRs uniaxial in a tensile test machine. In addition to the optical characterization of gold NRs and QDs, their thermal behavior in solution as well as in different nanocomposites is studied. A shortening of the gold NRs or a transformation into spherical gold NP is observed, if the polymer nanocomposites containing gold NRs are heated above a temperature of 200 °C. The PL of the synthesized gold QDs strongly depends on the ambient temperature. An increase of PL quantum yield (QY) and PL lifetime occur, if the solutions are cooled. The best PL QY of 16.6 % was observed for octadecyl mercaptan capped gold QDs at room temperature, which could be improved to 28.6 % when cooling the solutions to -7 °C. Furthermore, optically anisotropic security labels containing gold NRs and thermosensitive security devices containing gold QDs are developed. Due to their unique optical properties, gold NRs and QDs are interesting candidates for optoelectronical as well as data storage devices and medical applications like biomedical imaging or cancer therapy.

We explore a new laboratory technique in the field of urinalysis promising a combination of speed and selectivity in support of urinary tract infection diagnosis. Laboratory experimentation demonstrates long range surface plasmon polaritons (LRSPP) waveguides as a useful biosensor to selectively detect gram negative bacteria or gram positive bacteria in human urine. The biosensor can detect bacteria at concentration of 105 CFU/ml, the internationally recommended threshold for diagnostic of urinary tract infection (UTI). Using a negative control solution at bacterial concentration 1000x higher than the targeted bacteria in urine with a weak concentration of constituents, the power ratio between the negative control signals to the target bacteria signal is measured to be 5.4. Thus we report a conclusive demonstration of the LRSPP waveguide biosensor selectivity to the gram of bacteria in human urine. In addition, the biosensor may prove useful as an alternative urinalysis test method to determine the urine specific gravity, to estimate proteinuria, and to detect biofilm formation on surfaces.

Les plasmons de surface sont des quasi-particules résultant du couplage fort entre l'oscillation collective des porteurs libres d'un métal (plasma) et une onde électromagnétique. Ils sont générés à l'interface entre un métal et un diélectrique. Ils sont étudiés depuis plusieurs années pour leurs propriétés remarquables de confinement du champ électromagnétique à l'interface ou encore d'exaltation de ce même champ. Les plasmons de surface (SPP) sont à la base de la plasmonique, domaine qui exploite leurs propriétés optiques. L'une des caractéristiques principales des SPP est la fréquence plasma. Elle est proportionnelle à la densité de porteurs libres. La majorité des travaux effectués en plasmonique concerne les métaux nobles comme l'or ou l'argent. Cependant, leur utilisation est délicate dans certaines gammes de longueurs d'onde, telle que l'infrarouge, lorsqu'il est nécessaire d'exploiter l'exaltation du champ électrique pour la détection de molécules en biologie. Pour contrôler au mieux cet effet d'exaltation du champ électrique, il est nécessaire d'ajuster la fréquence plasma. Cela impossible pour les métaux nobles qui sont par ailleurs incompatibles avec les procédés actuels de la microélectronique. L'utilisation de semi-conducteurs fortement dopés en plasmonique permet de contourner ces limitations. En changeant le dopage ou le type de semi-conducteur, il est possible de changer la fréquence plasma du matériau et ainsi, d'obtenir des résonances plasmoniques dans le moyen infrarouge. Mon travail de thèse concerne la réalisation et la caractérisation de réseaux plasmoniques à base semi-conducteurs dopés. Les échantillons sont constitués d'une couche d'InAsSb (antimoniure d'arséniure et d'indium) dopée au silicium. Cette couche est déposée par épitaxie par jets moléculaires (MBE) sur un substrat de GaSb (antimoniure de gallium). Dans un premier temps j'ai mis au point un moyen de caractérisation rapide et non destructif du niveau de dopage dans les couches d'InAsSb et donc de la fréquence plasma, basé sur la réflectivité en angle. Un modèle théorique basé sur le mode de Brewster m'a permis d'expliquer les résultats expérimentaux. J'ai ensuite mis au point les étapes technologiques permettant de réaliser les rubans d'InAsSb. Elles sont basées sur de la lithographie interférentielle, la gravure chimique humide et la gravure sèche par plasma. En modifiant les dimensions du réseau, j'ai démontré la possibilité de contrôler les propriétés optiques des résonateurs plasmoniques. Enfin, nous avons fabriqué des réseaux d'InAsSb enterrés, en procédant à une reprise d'épitaxie par MBE d'une couche de GaSb sur le réseau InAsSb. Nous arrivons ainsi à planariser la structure en conservant sa cristallinité. J'ai donc démontré qu'il était possible d'intégrer des structures plasmoniques à des composants photoniques opérant dans l'infrarouge en utilisant seulement des semi-conducteurs. La voie est ouverte pour le développement d'une plasmonique infrarouge tout-semi-conducteurs. Mon travail de thèse est pionnier dans ce domaine. / Surface plasmons polaritons (SPP) are quasi-particles resulting from the strong coupling between the collective oscillations of free carriers in a metal and an electromagnetic wave. They are generated at the interface between a metal and a dielectric. They are studied in detail for several years for their outstanding properties of electromagnetic field confinement at the interface or of filed exaltation. SPP are the building blocks of plasmonics, the area that exploit their optical properties. One of the main characteristics of the SPP is the plasma frequency which is proportional to the density of free carriers. Plasmonics is essentially based on noble metals like gold or silver. However, noble metals are difficult to use in certain ranges of wavelengths, such as infrared, to exploit the electric field exaltation for the detection of molecules in biology. To improve the control of this electric field exaltation, it is necessary to adjust the plasma frequency. It impossible with noble metals that are otherwise incompatible with current microelectronics processes. To overcome these limitations we propose to use heavily doped semiconductors. By changing the doping or the type of the semiconductor, it is possible to change the plasma frequency and thus obtain plasmonic resonances in the mid-infrared. My work deals with the realization and the characterization of doped semiconductors plasmonic gratings. The samples consist of an InAsSb (indium, arsenide, antimonide) layer doped with silicon. This layer is deposited by molecular beam epitaxy (MBE) on a GaSb substrate (gallium antimonide). I have developed an experimental technique based angular dependent reflectivity of rapid and non-destructive characterization of the doping level in the InAsSb layers and thus the plasma frequency. A theoretical model based on Brewster modes allowed explaining the experimental results. I then developed a technological process to achieve the InAsSb gratings. They are based on interference lithography, chemical wet etching and dry plasma etching. By changing the size of the grating, I have demonstrated the ability to control the optical properties of plasmonic resonators. Finally, we have made of InAsSb grating buried into a GaSb layer, using a regrowth by MBE technique. The structure is planarized with a good crystallinity. So it is possible to integrate plasmonic resonators nearby photonic compounds operating in the infrared using only semiconductors. We pave the way for the development of all-semiconductor infrared plasmonics. My thesis is a pioneer work in this field.

Diplomová práce se zabývá fotoluminiscencí polovodičových materiálů zesílené plazmonovými polaritony. Je popsána základní teorie interakce mezi lokalizovanými povrchovými plazmonovými polaritony a fotoluminiscenčními látkami. Dva mechanismy, které mohou vést k fotoluminiscenci zesílené plazmonovými polaritony jsou diskutovány. Následně je popsán návrh aparatury pro měření fotoluminiscence a způsob její realizace. Funkčnost aparatury je ověřena měřením fotoluminiscenčních spekter objemového GaN, nanokrystalického Si a CdTe kvantových teček. Nakonec je zkoumána metoda přípravy vzorků sestávajících z kovových nanokuliček a fotoluminiscenčně aktívních CdTe kvantových teček.

We investigate field quantization in high-curvature geometries. The models and calculations can help with understanding the elastic and inelastic scattering of photons and electrons in nanostructures and probe-like metallic domains. The results find important applications in high-resolution photonic and electronic modalities of scanning probe microscopy, nano-optics, plasmonics, and quantum sensing. Quasistatic formulation, leading to nonretarded quantities, is employed and justified on the basis of the nanoscale, here subwavelength, dimensions of the considered domains of interest. Within the quasistatic framework, we represent the nanostructure material domains with frequency-dependent dielectric functions. Quantities associated with the normal modes of the electronic systems, the nonretarded plasmon dispersion relations, eigenmodes, and fields are then calculated for several geometric entities of use in nanoscience and nanotechnology. From the classical energy of the charge density oscillations in the modeled nanoparticle, we then derive the Hamiltonian of the system, which is used for quantization. The quantized plasmon field is obtained and, employing an interaction Hamiltonian derived from the first-order perturbation theory within the hydrodynamic model of an electron gas, we obtain an analytical expression for the radiative decay rate of the plasmons. The established treatment is applied to multiple geometries to investigate the quantized charge density oscillations on their bounding surfaces. Specifically, using one sheet of a two-sheeted hyperboloid of revolution, paraboloid of revolution, and cylindrical domains, all with one infinite dimension, and the finite spheroidal and toroidal domains are treated. In addition to a comparison of the paraboloidal and hyperboloidal results, interesting similarities are observed for the paraboloidal domains with respect to the surface modes and radiation patterns of a prolate spheroid, a finite geometric domain highly suitable for modeling of nanoparticles such as quantum dots. The prolate and oblate spheroidal calculations are validated by comparison to the spherical case, which is obtained as a special case of a spheroid. In addition to calculating the potential and field distributions, and dispersion relations, we study the angular intensity and the relation between the emission angle with the rate of radiative decay. The various morphologies are compared for their plasmon dispersion properties, field distributions, and radiative decay rates, which are shown to be consistent. For the specific case of a nanoring, modeled in the toroidal geometry, significant complexity arises due to an inherent coupling among the various modes. Within reasonable approximations to decouple the modes, we study the radiative decay channel for a vacuum bounded single solid nanoring by quantizing the fields associated with charge density oscillations on the nanoring surface. Further suggestions are made for future studies. The obtained results are relevant to other material domains that model a nanostructure such as a probe tip, quantum dot, or nanoantenna.