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Microfabrication of Plasmonic Biosensors in CYTOP Integrating a Thin SiO2 Diffusion and Etch-barrier LayerHanif, Raza 18 April 2011 (has links)
A novel process for the fabrication of Long Range Surface Plasmon Polariton (LRSPP) waveguide based biosensors is presented herein. The structure of the biosensor is comprised of Au stripe waveguide devices embedded in thick CYTOP claddings with a SiO2 solvent diffusion barrier and etch-stop layer. The SiO2 layer is introduced to improve the end quality of Au waveguide structures, which previously deformed during the deposit of the upper cladding process and to limit the over-etching of CYTOP to create micro-fluidic channels. The E-beam evaporation method is adapted to deposit a thin SiO2 on the bottom cladding of CYTOP. A new micro-fluidic design pattern is introduced. Micro-fluidic channels were created on selective Au waveguides through O2 plasma etching. The presented data and figures are refractive index measurements of different materials, thickness measurements, microscope images, and AFM images. Optical power cutback measurements were performed on fully CYTOP-cladded symmetric LRSPP waveguides. The end-fire coupling method was used to excite LRSPP modes with cleaved polarization maintaining (PM) fibre. The measured mode power attenuation (MPA) was 6.7 dB/mm after using index-matched liquid at input and output fibre-waveguide interfaces. The results were compared with the theoretical calculations and simulations. Poor coupling efficiency and scattering due to the SiO2 are suspected for off-target measurements.
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Gold nanoshells for surface enhanced Raman spectroscopy and drug deliveryJanuary 2012 (has links)
Gold nanoshells are tunable plasmonic nanostructures consisting of spherical silica cores wrapped with thin layer of Au. Based on the size of the Au layer with respect to the silica core, gold nanoshells can resonantly absorb or scatter light at any wavelength on the visible or infrared. On resonance, gold nanoshells interact strongly with light to give rise to collective oscillations of the free electrons against the background of the ionic core, phenomena known as localized surface plasmons. The free electron oscillation creates surface plasmon multimodes of various orders. As a result, the average local near field surrounding the Au nanoshell is enhanced. The local field enhancement has been extensively used in different applications. In this work, the local near-field is used to enhance the Raman spectroscopy of DNA and explore the different modes attributed to the base composition and structure of the DNA sequence. We showed that urface enhanced Raman spectroscopy of DNA is dominated by the adenine modes regardless of the base composition of the DNA sequence, a property that we have used to develop a DNA label-free detection system. As absorbers, plasmon-resonant Au nanoshells can convert absorbed light into heat. As a consequence, the temperature on the Au nanoshell surface increases dramatically. This property is used to light-trigger the release of variety of therapeutic molecules such as single stranded DNA, siRNA and small molecules. We demonstrated that the local heat can be used to dehybridize double stranded DNA attached to the Au surface via a thiol moiety on one of the DNA strands. The complementary sequence (therapeutic sequence) is released at temperature lower than the standard melting temperature of same DNA sequence. Moreover, small molecules (DAPI) which were initially intercalated on the double stranded DNA attached to the Au surface were successfully released due to the heat generated around the nanoshell surface. Finally, siRNA molecules were also released using a different system made of PLL (polylysine) attached to Au nanoshells. The electrostatic interaction between the negatively charged siRNA and the positively charged PLL was overcome by the thermal perturbation causing the siRNA to be released. In vitro experiments successfully showed the release of siRNA, single stranded DNA and small molecules.
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Optical Properties of Individual Nano-Sized Gold Particle Pairs / Optische Eigenschaften einzelner Gold-Nanopartikel-Paare / Mie-Scattering, Fluorescence, and Raman-ScatteringOlk, Phillip 13 August 2008 (has links) (PDF)
This thesis examines and exploits the optical properties of pairs of MNPs. Pairs of MNPs offer two further parameters not existent at single MNPs, which both affect the local optical fields in their vicinity: the distance between them, and their relative orientation with respect to the polarisation of the excitation light. These properties are subject of three chapters: One section examines the distance-dependent and orientation-sensitive scattering cross section (SCS) of two equally sized MNPs. Both near- and far-field interactions affect the spectral position and spectral width of the SCS. Far-field coupling affects the SCS even in such a way that a two-particle system may show both a blue- and redshifted SCS, depending only on the distance between the two MNPs. The maximum distance for this effect is the coherence length of the illumination source – a fact of importance for SCS-based experiments using laser sources. Another part of this thesis examines the near-field between two MNPs and the dependence of the locally enhanced field on the relative particle orientation with respect to the polarisation of the excitation light. To attain a figure of merit, the intensity of fluorescence light from dye molecules in the surrounding medium was measured at various directions of polarisation. The field enhancement was turned into fluorescence enhancement, even providing a means for sensing the presence of very small MNPs of 12 nm in diameter. In order to quantify the near-field experimentally, a different technique is devised in a third section of this thesis – scanning particle-enhanced Raman microscopy (SPRM). This device comprises a scanning probe carrying an MNP which in turn is coated with a molecule of known Raman signature. By manoeuvring this outfit MNP into the vicinity of an illuminated second MNP and by measuring the Raman signal intensity, a spatial mapping of the field enhancement was possible. / Diese Dissertation untersucht und nutzt die optischen Eigenschaften von Paaren von Metall-Nanopartikeln (MNP). MNP-Paare bieten gegenüber einzelnen MNP zwei weitere Parameter, welche beide auf das optische Nahfeld der zwei MNPs wirken: zum Einen der Abstand der zwei MNPs zueinander, zum Anderen die relative Ausrichtung des Paares bezüglich der Polarisation des anregenden Lichts. Diese Eigenschaften sind Thema der Arbeit: Ein Abschnitt untersucht den abstands- und orientierungsabhängigen Streuquerschnitt (SQS) zweier gleichgroßer MNPs. Die spektrale Position und die Breite des SQS wird von Wechselwirkungen sowohl im Nah- als auch im Fernfeld beeinflusst. Der Einfluß der Fernfeld-Wechselwirkung geht so weit, daß ein Zwei-MNP-System sowohl einen blau- als auch einen rotverschobenen SQS haben kann – dies hängt lediglich vom Abstand der zwei MNPs ab. Die Reichweite dieser Fernfeld-Wechselwirkung wird durch die Kohärenzlänge der Beleuchtungsquelle bestimmt – eine wichtige Tatsache für SQS-Untersuchungen, welche Laserquellen verwenden. Ein weiterer Teil der Dissertation untersucht das Nahfeld zwischen zwei MNPs. Insbesondere wird dargestellt, inwieweit die Überhöhung des Nahfelds von der Orientierung des Partikelpaares bezüglich der Polarisation des Anregungslichts abhängt. Um den Effekt quantifizieren zu können, wurde die Intensität der Fluoreszenz des umgebenden Mediums für verschiedene Polarisationsrichtungen gemessen. Die lokale Feldverstärkung konnte in eine Fluoreszenzverstärkung gewandelt werden, mit deren Hilfe sich sogar die Anwesenheit sehr kleiner MNPs von nur 12 nm Durchmesser nachweisen ließ. Wie Nahfeld-Intensitäten experimentell quantifiziert werden können, stellt ein dritter Abschnitt dieser Dissertation vor – per MNP-verstärkter Raman-Rastersonden-Mikroskopie. Diese Technik besteht aus einer Rastersonde, welcher ein MNP anheftet, welches wiederum mit einem Molekül bekannter Ramansignatur überzogen ist. Indem solch eine Sonde in die unmittelbare Nähe eines zweiten, beleuchteten MNPs gebracht wurde und dabei die Intensität des Raman-Signals aufgezeichnet wurde, ließ sich die räumliche Verteilung der Ramanverstärkung vermessen.
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Lichtauskopplung aus LEDs mittels MetallnanoteilchenGöhler, Tino 01 February 2011 (has links) (PDF)
Der externe Wirkungsquerschnitt von auf AlGaAs/InGaAlP basierenden Leuchtdioden (LEDs) ist auf Grund von Totalreflexion infolge des hohen Brechungsindex des Halbleitermaterials (n=3...4) beschränkt. Auf die Oberfläche der LED aufgebrachte metallische Nanoteilchen (MNT) können jedoch als Dipolstreuer genutzt werden, um so die Emission der LED zu vergrößern. In dieser Arbeit wurden zunächst einzelne Goldnanoteilchen verschiedener Größe auf einer solchen Leuchtdiode in zwei verschiedenen Der externe Wirkungsquerschnitt von auf AlGaAs/InGaAlP basierenden Leuchtdioden (LEDs) ist auf Grund von Totalreflexion infolge des hohen Brechungsindex des Halbleitermaterials (n=3...4) beschränkt. Auf die Oberfläche der LED aufgebrachte metallische Nanoteilchen (MNT) können jedoch als Dipolstreuer genutzt werden, um so die Emission der LED zu vergrößern. In dieser Arbeit wurden zunächst einzelne Goldnanoteilchen verschiedener Größe auf einer solchen Leuchtdiode in zwei verschiedenen Umgebungsmedien untersucht. Dabei zeigt sich eine deutliche Verstärkung der Emission, falls die Dipolresonanz des MNT bei kürzeren Wellenlängen im Vergleich zur LED-Emission liegt. Für den Fall, dass die Dipolresonanz mit der Emission überlappt oder bei größeren Wellenlängen liegt, kommt es zu einer Abschwächung. Numerische Berechnungen zeigen, dass dabei die Stärke der Quadrupolmode, welche zusätzliche Absorption hervorruft, sowie eine Rotverschiebung der Dipolresonanz bei Anregung oberhalb des kritischen Winkels der Totalreflexion eine entscheidende Rolle spielen. Mit Hilfe einer speziellen Maskentechnik, der Fischer-Pattern-Nanolithographie, können Arrays von MNT hergestellt und anschließend die MNT in Form und Größe manipuliert werden. Die zunächst dreieckige Form der Partikel führt zu einer Abschwächung der Emission, welche sich aber durch Umwandlung der MNT in Kugeln zu einer Emissionsverstärkung wendet. Dabei kann Licht, welches sonst im Substrat gefangen wäre, durch plasmonische Streuung ausgekoppelt werden. Eine Untersuchung ähnlicher Strukturen auf einem hochbrechenden, transparenten Substrat (GaP) zeigt, dass die Lage der plasmonischen Resonanzen stärker vom Abstand der Partikel abhängt, als gewöhnlich zu erwarten wäre. / The external quantum efficiency of light-emitting diodes (LEDs) based on AlGaAs/InGaAlP is limited by total internal reflection because of the high refractive index (typically between 3 and 4) of the semiconductor. Metal nanoparticles (MNP) deposited on the surface of the LED can be used as dipole scatterers in order to enhance the emission of the LED. In this thesis, first, single gold nanoparticles of various sizes deposited on such an LED were investigated. A clear enhancement is detected as long as the dipole plasmon resonance of the particle is at a shorter wavelength than the LED emission. If the plasmon resonance coincides with the LED emission or is at a larger wavelength, the enhancement turns into suppression. Numerical simulations indicate that this latter effect is mainly caused by the particle quadrupole resonance producing extra absorption.
Arrays of MNPs can be produced by a special mask technique called \"Fischer pattern nanolithography\" and manipulated in shape and size by additional steps. Originally, the MNPs produced by this technique are triangular in shape and turn out to suppress the LED emission. After transformation of the particles to spheres, a clear enhancement was detected. Light that would otherwise remain trapped inside the substrate is coupled out by resonant plasmonic scattering. Investigations on analogous structures on a transparent high-index material (GaP) indicate a stronger coupling between the particles than expected on the basis of literature data.
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Tailoring nanoscale metallic heterostructures with novel quantum propertiesSanders, Charlotte E. 2013 May 1900 (has links)
Silver (Ag) is an ideal low-loss platform for plasmonic applications, but from a materials standpoint it presents challenges. Development of plasmonic devices based on Ag thin film has been hindered both by the dificulty of fabricating such film and by its fragility out of vacuum. Silver is non-wetting on semiconducting and insulating substrates, but on certain semiconductors and insulators can adopt a metastable atomically at epitaxial film morphology if it is deposited using the "two-step" growth method. This method consists of deposition at low temperature and annealing to room temperature. However, epitaxial Ag is metastable, and dewets out of vacuum. The mechanisms of dewetting in this system remain little understood. The fragility of Ag film presents a particular problem for the engineering of plasmonic devices, which are predicted to have important industrial applications if robust low-loss platforms can be developed. This dissertation presents two sets of experiments. In the first set, scanning probe techniques and low energy electron microscopy have been used to characterize Ag(111) growth and dewetting on two orientations of silicon (Si), Si(111) and Si(100). These studies reveal that multiple mechanisms contribute to Ag film dewetting. Film stability is observed to increase with thickness, and thickness to play a decisive role in determining dewetting processes. A method has been developed to cap Ag film with germanium (Ge) to stabilize it against dewetting. The second set of experiments consists of optical studies that focus on the plasmonic properties of epitaxial Ag film. Because of the problems posed until now by epitaxial Ag growth and stabilization, research and development in the area of plasmonics has been limited to devices based on rough, thermally evaporated Ag film, which is robust and simple to produce. However, plasmonic damping in such film is higher than in epitaxial film. The optical studies presented here establish that Ag film can now be stabilized sufficiently to allow optical probing and device applications out of vacuum. Furthermore, they demonstrate the superiority of epitaxial Ag film relative to thermally evaporated film as a low-loss platform for plasmonic devices spanning the visible and infrared regimes. / text
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Nonlinear and wavelength-tunable plasmonic metasurfaces and devicesLee, Jongwon 15 January 2015 (has links)
Wavelength-tunable optical response from solid-state optoelectronic devices is a desired feature for a variety of applications such as spectroscopy, laser emission tuning, and telecommunications. Nonlinear optical response, on the other hand, has an important role in modern photonic functionalities, including efficient frequency conversions, all-optical signal processing, and ultrafast switching. This study presents the development of optical devices with wavelength tunable or nonlinear optical functionality based on plasmonic effects. For the first part of this study, widely wavelength tunable optical bandpass filters based on the unique properties of long-range surface plasmon polaritons (LR SPP) are presented. Planar metal stripe waveguides surrounded by two different cladding layers that have dissimilar refractive index dispersions were used to develop a wide wavelength tuning. The concept was demonstrated using a set of index-matching fluids and over 200nm of wavelength tuning was achieved with only 0.004 of index variation. For practical application of the proposed concept, a thermo-optic polymer was used to develop a widely tunable thermo-optic bandpass filter and over 220 nm of wavelength tuning was achieved with only 8 ºC of temperature variation. Another novel approach to produce a widely wavelength tunable optical response for free-space optical applications involves integrating plasmonic metasurfaces with quantum-electronic engineered semiconductor layers for giant electro-optic effect, which is proposed and experimentally demonstrated in the second part of this study. Coupling of surface plasmon modes formed by plasmonic nanoresonators with Stark tunable intersubband transitions in multi-quantum well structures induced by applying bias voltages through the semiconductor layer was used to develop tunable spectral responses in the mid-infrared range. Experimentally, over 310 nm of spectral peak tuning around 7 μm of wavelength with 10 ns response time was achieved. As the final part of this study, highly nonlinear metasurfaces based on coupling of electromagnetically engineered plasmonic nanoresonators with quantum-engineered intersubband nonlinearities are proposed and experimentally demonstrated. In the proof-of-concept demonstration, an effective nonlinear susceptibility over 50 nm/V was measured and, after further optimization, over 480 nm/V was measured for second harmonic generation under normal incidence. The proposed concept shows that it is possible to engineer virtually any element of the nonlinear susceptibility tensor of the nonlinear metasurface. / text
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Microfabrication of Plasmonic Biosensors in CYTOP Integrating a Thin SiO2 Diffusion and Etch-barrier LayerHanif, Raza 18 April 2011 (has links)
A novel process for the fabrication of Long Range Surface Plasmon Polariton (LRSPP) waveguide based biosensors is presented herein. The structure of the biosensor is comprised of Au stripe waveguide devices embedded in thick CYTOP claddings with a SiO2 solvent diffusion barrier and etch-stop layer. The SiO2 layer is introduced to improve the end quality of Au waveguide structures, which previously deformed during the deposit of the upper cladding process and to limit the over-etching of CYTOP to create micro-fluidic channels. The E-beam evaporation method is adapted to deposit a thin SiO2 on the bottom cladding of CYTOP. A new micro-fluidic design pattern is introduced. Micro-fluidic channels were created on selective Au waveguides through O2 plasma etching. The presented data and figures are refractive index measurements of different materials, thickness measurements, microscope images, and AFM images. Optical power cutback measurements were performed on fully CYTOP-cladded symmetric LRSPP waveguides. The end-fire coupling method was used to excite LRSPP modes with cleaved polarization maintaining (PM) fibre. The measured mode power attenuation (MPA) was 6.7 dB/mm after using index-matched liquid at input and output fibre-waveguide interfaces. The results were compared with the theoretical calculations and simulations. Poor coupling efficiency and scattering due to the SiO2 are suspected for off-target measurements.
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Untersuchungen zur effizienten Herstellung von Substraten für die oberflächenverstärkte InfrarotspektroskopieKatzmann, Julia 12 January 2016 (has links) (PDF)
Metallische Nanostäbe mit einer Länge im Mikrometer-Bereich wirken als Antennen für infrarotes Licht: Indem unter Lichteinfall eine kollektive Schwingung der Leitungselektronen angeregt wird (ein sogenanntes Plasmon), wird das elektrische Feld an den Stabenden stark konzentriert. Besonders starke Feldkonzentrationen treten auf, wenn zwei Antennenarme durch eine schmale Lücke getrennt sind (Dimerantenne). Somit können die Antennen Licht-Materie-Wechselwirkungen -- wie beispielsweise die Absorption infraroten Lichtes von Molekülen -- verstärken. Dieses als oberflächenverstärkte Infrarotabsorption (SEIRA) bezeichnete Phänomen ist sehr nützlich, um Signale in der Infrarotspektroskopie zu verstärken.
Diese Arbeit widmet sich der effizienten Herstellung von metallischen Nanostäben für SEIRA. Im ersten Schwerpunktthema werden Dimerantennen, die per Elektronenstrahllithographie (EBL) hergestellt wurden und eine auflösungsbegrenzte Lücke aufweisen, durch eine photochemische Reduktion von Metallsalzkomplexen nachträglich vergrößert. Dadurch verringert sich die Lückengröße und erreicht Werte deutlich unter der Auflösungsgrenze der EBL. Es wird gezeigt, dass diese photochemische Abscheidung die IR-optischen Eigenschaften der Dimerantennen durch plasmonische Kopplung entscheidend verändert. Zudem steigt die Infrarotabsorption von in der Lücke befindlichen Molekülen mit sinkender Lückengröße.
Im zweiten Schwerpunktthema liegt der Fokus auf der günstigen Fabrikation einer Vielzahl von IR-Antennen in einem parallelen Prozess. Dabei werden poröse Template aus anodisiertem Aluminiumoxid (AAO) als Negativ für die herzustellenden Metallstäbe benutzt. Es wird zuerst gezeigt, dass die Poren des Templates durch die photochemische Reduktion von Goldsalzkomplexen befüllt werden können. Für eine gezielte Einstellung der Stäbchenlänge und die Generierung einer nanoskaligen Lücke wird weiterhin die elektrochemische Befüllung der Template untersucht. Die hiermit hergestellten IR-Antennen werden vereinzelt, auf ein Substrat aufgetragen und hinsichtlich ihrer Struktur und ihrer IR-optischen Eigenschaften charakterisiert.
Die Vor- und Nachteile der untersuchten Herstellungsmethoden und ihre Eignung für die Fabrikation von IR-Antennen für SEIRA werden diskutiert. / Metallic nanorods with lengths in the micrometer regime act as antennas for infrared light: As incident light excites a collective oscillation of the conduction electrons (a so-called plasmon), the electric field is concentrated at the rod ends. In case two antenna arms are separated by a small gap (dimer antenna), a particularly high field concentration occurs. Thereby the antennas are capable of enhancing light-matter-interaction -- for example the absorption of infrared light by molecules. This phenomenon, termed as surface enhanced infrared absorption (SEIRA), is very useful to enhance absorption signals in infrared spectroscopy.
This thesis attends to the efficient fabrication of metallic nanorods for SEIRA. The first topic in focus is the manipulation of dimer antennas fabricated by electron beam lithography (EBL), featuring a gap of resolution-limited size. By applying a photochemical reduction of metal salt complexes in solution, the dimer arms are subsequently enlarged. Thereby the gap size is reduced and reaches values clearly below the resolution limit of EBL. It is shown that the IR optical properties of dimer antennas dramatically change during photochemical metal deposition. This is due to plasmonic coupling. Additionally, the absorption of infrared light by molecules located in the gap increases with decreasing gap size.
The second topic in focus is the cheap fabrication of a large number of IR antennas in a parallel process. Here, porous templates of anodized aluminum oxide (AAO) are used as a negative for the metal rods to be fabricated. Firstly, it is shown that the pores of the template can be filled by photochemical reduction of gold salt complexes. For a targeted adjustment of the rod lengths and the generation of a nanoscale gap, secondly, the electrochemical filling of acsu AAO is investigated. The IR antennas prepared by this method are extracted from the template, transferred to a substrate, and individually characterized in terms of their structure and IR optical properties.
Advantages and drawbacks of the fabrication methods investigated in this work as well as their applicability to the fabrication of IR antennas for SEIRA are being discussed.
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Fonctionnalisation de surface de résonateurs plasmoniques à base de semi-conducteur III-V pour la spectroscopie vibrationnelle exaltée / Surface functionalization of plasmonic III-V semiconductors for surface-enhanced vibrational spectroscopyBomers, Mario 13 July 2018 (has links)
Cette thèse traite de la fonctionnalisation de surface des résonateurs plasmonique à base de semi-conducteur III-V en utilisant de l’acide phosphonique pour la spectroscopie vibrationnelle exaltée permettant d'identifier des quantités infimes de molécules. Le premier chapitre décrit les fondements théoriques de la spectroscopie vibrationnelle exaltée. En comparant les propriétés plasmoniques du semi-conducteur dégénéré InAs(Sb):Si et des métaux, ici l’or et le gallium, on trouve que l’InAs(Sb):Si est particulièrement adapté à la spectroscopie infrarouge exaltée (SEIRA) et que le gallium est adapté à la spectroscopie Raman exaltée (SERS). Les deux matériaux plasmoniques alternatifs surpassent théoriquement l'or dans leurs gammes spectrales respectives. Néanmoins, l'or et son inertie chimique restent intéressants pour permettre la spectroscopie vibrationnelle exaltée dans différents environnements chimiques.Dans le deuxième chapitre on démontre que l’InAs(Sb):Si est chimiquement stable dans l'eau, contrairement au GaSb. Une structure en couches composites de GaSb/InAsSb:Si a été utilisée pour montrer que la déplétion de l'antimoine et l'incorporation d'oxygène à l'interface GaSb-eau transforment, en un peu moins de 14 h, 50 nm de GaSb cristallin en un oxyde de gallium. Cet oxyde de gallium a un indice de réfraction moyen-IR de l'ordre de n=1,6 ce qui est environ la moitié de la valeur de l'indice de réfraction du GaSb dans le moyen-IR.Dans le troisième chapitre, on démontre que cette modification de l'indice de réfraction lors de l'oxydation peut être exploitée pour décaler la résonance plasmonique localisée des réseaux InAsSb:Si sur des substrats GaSb dans la plage de 5 µm à 20 µm par formation d’un piédestal.Dans le chapitre 4 est présenté le contrôle de la liaison chimique des molécules organiques avec la fine couche d'oxyde natif à la surface du semi-conducteur III-V. L’attachement de ces molécules sur l’oxyde de surface ouvre la voie à des applications bio-photoniques utilisant des semi-conducteurs améliorés par des résonateurs plasmoniques.Dans le chapitre 5 est décrit deux stratégies différentes pour combiner des résonateurs plasmoniques à base de III-V avec des circuits micro-fluidiques. Ces résultats démontrent que des applications lab-on-the-chip basées sur des semi-conducteurs III-V sont possibles.Enfin, la possibilité d'intégrer des nanoparticules de Gallium plasmoniques sur des semi-conducteurs III-V pour combiner les méthodes SEIRA et SERS est présentée au chapitre 6. / This thesis deals with the surface functionalization of nanostructured plasmonic III-V semiconductors for surface-enhanced vibrational spectroscopy relevant to identify minute amounts of analyte molecules.The first chapter outlines the theoretical foundations of surface-enhanced vibrational spectroscopy based on plasmonics. Comparing the plasmonic properties of the degenerate semiconductor InAs(Sb):Si and of metals, here gold and gallium, it is found that the degenerate semiconductor is especially suited for surface-enhanced infrared (SEIRA) spectroscopy and that gallium with its plasmonic potential in the UV-VIS range is apt for surface-enhanced Raman spectroscopy (SERS). Both alternative plasmonic materials theoretically outperform gold in their respective spectral ranges. Nevertheless, gold and its chemical inertness remain interesting for enabling plasmonic enhanced vibrational spectroscopy in different chemical environments. The influence of aqueous environments on the material properties of III-V semiconductors is addressed in the second and in the third chapter. It is found that InAs(Sb):Si is chemical stable in water, but GaSb is not. A GaSb/InAsSb:Si compound layer structure was used to demonstrate that the depletion of antimony and the incorporation of oxygen at the GaSb-water interface transform 50 nm of crystalline GaSb to a gallium oxide in less than 14 hours. The gallium oxide has a mid-IR refractive index in the order of n=1.6 and thus less than half of the value of the mid-IR refractive index of GaSb. This change in refractive index upon oxidation can be exploited to blue-shift the localized plasmonic resonance of InAsSb:Si gratings on GaSb-substrates in the range from 5 µm to 20 µm by pedestal formation.In Chapter 4, the controlled chemical bonding of organic molecules to the approximately 3 nm thin native oxide layer of III-V semiconductor surfaces by phosphonic acid chemistry is presented. This paves the way for plasmonic enhanced all-semiconductor mid-IR biophotonic applications. In chapter 5, two different, but equally successful strategies to combine III-V based plasmonic resonators with microfluidic circuits are described. These results demonstrate that lab-on-the-chip applications based on III-V semiconductors are possible. Finally, the possibility to integrate plasmonic Gallium nanoparticles onto the III-V material platform for a potential combination of SEIRA and SERS applications is presented in chapter 6.
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[en] STUDY OF THE ALIGNMENT DYNAMICS OF GOLD NANORODS UNDER THE INFLUENCE OF AN EXTERNAL ELECTRICAL FIELD / [pt] ESTUDO DA DINÂMICA DE ALINHAMENTO DE NANOBASTÕES DE OURO SOB EFEITO DE UM CAMPO ELÉTRICO EXTERNOLEONARDO DE FARIAS ARAUJO 09 January 2019 (has links)
[pt] Cristais líquidos são amplamente utilizados atualmente em telas e filtros. Contudo, o alinhamento dos cristais líquidos possui uma resposta relativamente lenta (da ordem de milissegundos) devido à necessidade da interação entre vizinhos próximos. Em contrapartida, nanobastões de ouro são capazes de alinhar-se a um campo elétrico, mesmo quando isolados, devido à sua susceptibilidade elétrica elevada comparada a dos cristais líquidos, apresentando uma resposta de alinhamento significativamente mais rápida que a dos cristais líquidos. A forma alongada dos nanobastões faz com que sua absorção e seu espalhamento de luz, ocasionados pelo efeito de Ressonância de Plasmon de Superfície Localizado (Localized Surface Plasmon Resonance – LSPR), sejam altamente dependentes da orientação relativa dos nanobastões à polarização da luz incidente. Por isso, suspensões de nanobastões têm se tornado um novo paradigma em controle de luz por alinhamento induzido por campo elétrico. Neste trabalho, é apresentado um estudo da dinâmica de alinhamento dos nanobastões, por meio de medidas de transmissão de luz por um componente que permite a interação da luz com a suspensão de nanobastões enquanto sob influência de um campo elétrico de alinhamento. Foi encontrado um tempo de resposta de 1,5 microssegundos, 3 ordens de grandeza mais rápido que o de cristais líquidos comuns. Um segundo experimento foi realizado com um componente com dois pares de eletrodos transversais, no qual foi possível eliminar a relaxação lenta do sistema, demonstrando assim um chaveamento óptico digital com tempo de resposta da ordem de 110 Newton vezes segundo. Dois modelos teóricos foram propostos para descrever a dinâmica de alinhamento dos nanobastões e foi demonstrado que ambos os modelos ajustam bem os dados experimentais. Apresentamos também uma relação de equivalência entre os dois modelos. / [en] Liquid crystals are widely used nowadays in displays and optical filters. However, the alignment of liquid crystals has a relatively slow switching response (of the order of milliseconds) due to the near-neighbor interaction. In contrast, the high electrical susceptibility of a single gold nanorod enables its alignment to an external electric field, presenting a significantly faster switching response than that of liquid crystals. The elongated form of the nanorods makes their absorption and scattering, caused by the Localized Surface Plasmon Resonance (LSPR) effect, to be highly dependent on their orientation relative to the light polarization. Therefore, gold nanorod suspensions have become a new paradigm in light control by electric field-induced alignment. In this work, a study of the alignment dynamics of nanorods is presented, by means of light transmission measurements by a component that allows the interaction of light with the suspension of nanorods while under the influence of an electric field of alignment. An alignment time of 1.5 microseconds was found, which is 3 orders of magnitude smaller than traditional liquid crystal alignment mechanism response time. A second experiment was carried out with a component with two pairs of transverse electrodes, in which it was possible to eliminate the slow relaxation of the system, thus demonstrating a digital optical switch with response of the order of 110 Newton second. Two theoretical models were proposed to describe the alignment dynamics of the nanorods and it was demonstrated that both models fit well the experimental data. An equivalence relation between the two models is presented.
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