Amalgamations are a promising replacement for electronic solders, thermal interface materials, and other conductive joining materials. Amalgams are mechanically alloyed materials of a liquid constituent with a solid powder. Unlike traditional solders, these materials are processed at room temperature or slightly above, and can often operate at temperatures near, or beyond, their processing temperatures. Existing bonding processes require an excessive amount of heat, which may cause thermal stress to the electronic components and delaminate the attachment. Amalgams have promising characteristics for thermal interface materials (TIMs) due to being fully metallic, relatively easy of handling, and possessing metallic strength similar to solder or braze. Non-toxic gallium (Ga) based room temperature liquid metal alloys are a favorable material for structural amalgamations over conventional mercury (Hg). Unlike Hg amalgamations, Ga-based amalgamations have not been widely studied in the literature. In this work, the authors investigate a novel Ga-based amalgamation, further detailing the fabrication process and characterize the physical structure, chemistry, and mechanical strength. Different packing ratios are examined, by weight, 2:1, 1:1, 4:3, and 4:1 of Galinstan, which is composed of 68wt% Ga, 22wt% indium (In), 10wt% tin (Sn), to copper (Cu) powder. These ratios are molded into three-dimensional (3D) printed tensile bars of the American Society of Testing and Materials (ASTM) standard dimensions of a model that is per D638 TypeIV. The tensile bars are cured for 24-hours at three different temperatures (room temperature, 100°C, 200°C). The 4:1 ratio was the only specimen that failed to solidify. After allowing 24-hours of undisturbed curing, the samples that solidified were tested for their ultimate tensile strength. The optimal strength was achieved with the 2:1 ratio cured at 100°C, reaching an average tensile strength of 32.0 MPa. A scanning electron microscope (SEM), equipped with energy dispersive spectroscopy (EDS), was then utilized to perform microstructural characterization and local chemical composition mapping of fractured and polished sample surfaces. It is concluded that, of the packing ratios that set, there is no statistically significant correlation between packing ratio and tensile strength. Further, the phases formed during curing at room temperature are the same for all packing ratios but are present at different dispersions. However, it is found that the tensile strength decreases with statistical significance as the cure temperature is increased to 200°C. This change can be attributed to the presence of new phases that occur when the sample is heated to 200°C vs. when cured at room temperature. In the room temperature sample, x-ray diffraction (XRD) revealed the existence of pure Cu, CuGa2, and In3Sn. At 200°C, XRD shows a decrease in pure Cu, the presence of CuGa2 and In3Sn, and the emergence of a new Cu2Ga phase. These different phases form different interfaces with different bond energies, resulting in a change in tensile strength.

No description available.

The present work has been focused on the growth of Group III-nitride epitaxial layers and nanostructures on Si (111) substrates by plasma-assisted molecular beam epitaxy. Silicon is regarded as a promising substrate for III-nitrides, since it is available in large quantity, at low cost and compatible to microelectronics device processing. However, three-dimensional island growth is unavoidable for the direct growth of GaN on Si (111) because of the extreme lattice and thermal expansion coefficient mismatch. To overcome these difficulties, by introducing β-Si3N4 buffer layer, the yellow luminescence free GaN can be grow on Si (111) substrate. The overall research work carried out in the present study comprises of five main parts. In the first part, high quality, crack free and smooth surface of GaN and InN epilayers were grown on Si(111) substrate using the substrate nitridation process. Crystalline quality and surface roughness of the GaN and InN layers are extremely sensitive to nitridation conditions such as nitridation temperature and time. Raman and PL studies indicate that the GaN film obtained by the nitridation sequences has less tensile stress and optically good. The optical band gaps of InN are obtained between ~0.73 to 0.78 eV and the blueshift of absorption edge can be induced by background electron concentration. The higher electron concentration brings in the larger blueshift, due to a possible Burstein–Moss effect. InN epilayers were also grown on GaN/Si(111) substrate by varying the growth parameters such as indium flux, substrate temperature and RF power. In the second part, InGaN/Si, GaN/Si3N4/n-Si and InN/Si3N4/n-Si heterostructures were fabricated and temperature dependent electrical transport behaviors were studied. Current density-voltage plots (J-V-T) of InGaN/Si heterostructure revealed that the ideality factor and Schottky barrier height are temperature dependent and the incorrect values of the Richardson’s constant produced, suggests an inhomogeneous barrier at the heterostructure interface. The higher value of the ideality factor compared to the ideal value and its temperature dependence suggest that the current transport is primarily dominated by thermionic field emission rather than thermionic emission. The valence band offset of GaN/β-Si3N4/Si and InGaN/Si heterojunctions were determined by X-ray photoemission spectroscopy. InN QDs on Si(111) substrate by droplet epitaxy and S-K growth method were grown in the third part. Single-crystalline structure of InN QDs (droplet epitaxy) was verified by TEM and the chemical bonding configurations of InN QDs were examined by XPS. The interdigitated electrode pattern was created and (I-V) characteristics of InN QDs were studied in a metal–semiconductor–metal configuration in the temperature range of 80–300 K. The I-V characteristics of lateral grown InN QDs were explained by using the trap model. A systematic manipulation of the morphology, optical emission and structural properties of InN/Si (111) QDs (S-K method) is demonstrated by changing the growth kinetics parameters such as flux rate and growth time. The growth kinetics of the QDs has been studied through the scaling method and observed that the distribution of dot sizes, for samples grown under varying conditions, has followed the scaling function. In the fourth part, InN nanorods (NRs) were grown on Si(111) and current transport properties of NRs/Si heterojunctions were studied. The rapid rise and decay of infrared on/off characteristics of InN NRs/Si heterojunction indicate that the device is highly sensitive to the IR light. Self-aligned GaN nanodots were grown on semi-insulating Si(111) substrate. The interdigitated electrode pattern was created on nanodots using photolithography and dark as well as UV photocurrent were studied. Surface band gaps of InN QDs were estimated from scanning tunneling spectroscopy (STS) I-V curves in the last part. It is found that band gap is strongly dependent on the size of InN QDs. The observed size-dependent STS band gap energy blueshifts as the QD’s diameter or height was reduced.

It is well known that nanostructures possess unique electronic, optical, magnetic, ferroelectric and piezoelectric properties that are often superior to traditional bulk materials. In particular, one dimensional (1D) nanostructured inorganic materials including nanofibres, nanotubes and nanobelts have attracted considerable attention due to their distinctive geometries, novel physical and chemical properties, combined effects and their applications to numerous areas. Metal ion doping is a promising technique which can be utilized to control the properties of materials by intentionally introducing impurities or defects into a material. γ-Alumina (Al2O3), is one of the most important oxides due to its high surface area, mesoporous properties, chemical and thermal properties and its broad applications in adsorbents, composite materials, ceramics, catalysts and catalyst supports. γ-Alumina has been studied intensively over a long period of time. Recently, considerable work has been carried out on the synthesis of 1D γ-alumina nanostructures under various hydrothermal conditions; however, research on the doping of alumina nanostructures has not been forthcoming. Boehmite (γ-AlOOH) is a crucial precursor for the preparation of γ-Alumina and the morphology and size of the resultant alumina can be manipulated by controlling the growth of AlOOH. Gallium (Ga) is in the same group in the periodic table as aluminum. β-Gallium (III) oxide (β-Ga2O3), a wide band gap semiconductor, has long been known to exhibit conduction, luminescence and catalytic properties. Numerous techniques have been employed on the synthesis of gallium oxide in the early research. However, these techniques are plagued by inevitable problems. It is of great interest to explore the synthesis of gallium oxide via a low temperature hydrothermal route, which is economically efficient and environmentally friendly. The overall objectives of this study were: 1) the investigation of the effect of dopants on the morphology, size and properties of metal ion doped 1D alumina nanostructures by introducing dopant to the AlOOH structure; 2) the investigation of impacts of hydrothermal conditions and surfactants on the crystal growth of gallium oxide nanostructures. To achieve the above objectives, trivalent metal elements such as iron, gallium and yttrium were employed as dopants in the study of doped alumina nanostructures. In addition, the effect of various parameters that may affect the growth of gallium oxide crystals including temperature, pH, and the experimental procedure as well as different types of surfactants were systematically investigated. The main contributions of this study are: 1) the systematic and in-depth investigation of the crystal growth and the morphology control of iron, gallium and yttrium doped boehmite (AlOOH) under varying hydrothermal conditions, as a result, a new soft-chemistry synthesis route for the preparation of one dimensional alumina/boehmite nanofibres and nanotubes was invented; 2) systematic investigation of the crystal growth and morphology and size changes of gallium oxide hydroxide (GaOOH) under varying hydrothermal conditions with and without surfactant at low temperature; We invented a green hydrothermal route for the preparation of α-GaOOH or β-GaOOH micro- to nano-scaled particles; invented a simple hydrothermal route for the direct preparation of γ-Ga2O3 from aqueous media at low temperature without any calcination. The study provided detailed synthesis routes as well as quantitative property data of final products which are necessary for their potential industrial applications in the future. The following are the main areas and findings presented in the study: • Fe doped boehmite nanostructures This work was undertaken at 120ºC using PEO surfactant through a hydrothermal synthesis route by adding fresh iron doped aluminium hydrate at regular intervals of 2 days. The effect of dopant iron, iron percentage and experimental procedure on the morphology and size of boehmite were systematically studied. Iron doped boehmite nanofibres were formed in all samples with iron contents no more than 10%. Nanosheets and nanotubes together with an iron rich phase were formed in 20% iron doped boehmite sample. A change in synthesis procedure resulted in the formation of hematite large crystals. The resultant nanomaterials were characterized by a combination of XRD, TEM, EDX, SAED and N2 adsorption analysis. • Growth of pure boehmite nanofibres/nanotubes The growth of pure boehmite nanofibres/nanotubes under different hydrothermal conditions at 100ºC with and without PEO surfactant was systematically studied to provide further information for the following studies of the growth of Ga and Y doped boehmite. Results showed that adding fresh aluminium hydrate precipitate in a regular interval resulted in the formation of a mixture of long and short 1D boehmite nanostructures rather than the formation of relatively longer nanofibres/nanotubes. The detailed discussion and mechanism on the growth of boehmite nanostructure were presented. The resultant boehmite samples were also characterized by N2 adsorption to provide further information on the surface properties to support the proposed mechanism. • Ga doped boehmite nanostructures Based on this study on the growth of pure boehmite nanofibre/nanotubes, gallium doped boehmite nanotubes were prepared via hydrothermal treatment at 100ºC in the presence of PEO surfactant without adding any fresh aluminium hydrate precipitate during the hydrothermal treatment. The effect of dopant gallium, gallium percentage, temperature and experimental procedure on the morphology and size of boehmite was systematically studied. Various morphologies of boehmite nanostructures were formed with the increase in the doping gallium content and the change in synthesis procedure. The resultant gallium doped boehmite nanostructures were characterized by TEM, XRD, EDX, SAED, N2 adsorption and TGA. • Y doped boehmite nanostructures Following the same synthesis route as that for gallium doped boehmite, yttrium doped boehmite nanostructures were prepared at 100ºC in the presence of PEO surfactant. From the study on iron and gallium doped boehmite nanostructures, it was noted both iron and gallium cannot grow with boehmite nanostructure if iron nitrate and gallium nitrate were not mixed with aluminium nitrate before dissolving in water, in particular, gallium and aluminium are 100% miscible. Therefore, it’s not necessary to study the mixing procedure or synthesis route on the formation of yttrium doped boehmite nanostructures in this work. The effect of dopant yttrium, yttrium percentage, temperature and surfactant on the morphology and size of boehmite were systematically studied. Nanofibres were formed in all samples with varying doped Y% treated at 100ºC; large Y(OH)3 crystals were also formed at high doping Y percentage. Treatment at elevated temperatures resulted in remarkable changes in size and morphology for samples with the same doping Y content. The resultant yttrium doped boehmite nanostructures were characterized by TEM, XRD, EDX, SAED, N2 adsorption and TGA. • The synthesis of Gallium oxide hydroxide and gallium oxide with surfactant In this study, the growth of gallium oxide hydroxide under various hydrothermal conditions in the presence of different types of surfactants was systematically studied. Nano- to micro-sized gallium oxide hydroxide was prepared. The effect of surfactant and synthesis procedure on the morphology of the resultant gallium oxide hydroxide was studied. β-gallium oxide nanorods were derived from gallium oxide hydroxide by calcination at 900ºC and the initial morphology was retained. γ-gallium oxide nanotubes up to 65 nm in length, with internal and external diameters of around 0.8 and 3.0 nm, were synthesized directly in solution with and without surfactant. The resultant nano- to micro-sized structures were characterized by XRD, TEM, SAED, EDX and N2 adsorption. • The synthesis of gallium oxide hydroxide without surfactant The aim of this study is to explore a green synthesis route for the preparation of gallium oxide hydroxide or gallium oxide via hydrothermal treatment at low temperature. Micro to nano sized GaOOH nanorods and particles were prepared under varying hydrothermal conditions without any surfactant. The resultant GaOOH nanomaterials were characterized by XRD, TEM, SAED, EDX, TG and FT-IR. The growth mechanism of GaOOH crystals was proposed.

The present work demonstrates how a peptide-based material can be obtained for the biosorptive recovery of metals from contaminated industrial wastewater. Starting with Phage surface display for the initial identification and optimization of gallium-binding peptides, all the following application-focussed experiments are based on chemically synthesized peptides. Two chromatography-based biopanning methods for the identification of gallium-binding peptides from a commercial phage display library were developed. Five gallium-binding peptide sequences were identified and evaluated to show good gallium-binding properties. Furthermore, the biosorption of free gallium and arsenic by gallium-binding bacteriophage clones was investigated. A large influence of the pH-value on the respective interactions was demonstrated. Mutagenesis experiments were also carried out for a bacteriophage clone expressed peptide, in which a cysteine pair systematically replaced amino acids. Biosorption experiments with the resulting seven different bacteriophage mutants suggested a relationship between the rigidity of the peptide structure and the gallium-binding properties. In isothermal titration experiments, the thermodynamics of the interaction between gallium and the peptides as chemically synthesized derivatives were characterized, independent of the bacteriophage. The peptides differed strongly in their interaction with gallium, and in some cases, the complex formation with gallium depended strongly on the surrounding buffer conditions. The peptide with the amino acid sequence NYLPHQSSSPSR has particularly promising gallium-binding properties. Computer modeling suggests the probable structure of the peptide in aqueous solution and postulates a possible binding site for gallium. The side-selective and covalent immobilization of the peptides on a polystyrene matrix led to the creation of a biocomposite for the biosorptive recovery of gallium. The sorption performance and desorbability of the peptide-based biosorption materials were determined in studies with model solutions and real waters from the semiconductor industry.  :EIDESSTATTLICHE VERSICHERUNG II SUMMARY 7 CHAPTER I. 8 Utility of biotechnological approaches in resource technology 9 Phage Surface Display for the recovery of inorganic binding peptides 14 Gallium – Example of a high-tech metal 22 Aims and context of the present work 22 CHAPTER II. 25 Author contributions 25 Abstract 25 Introduction 26 Materials and Methods 28 2.1 Phage Display Library system 28 2.2 Biopanning experiments 29 2.3 Single clone identification 31 2.4 Single clone binding studies 31 Results 32 3.1 Immobilization of gallium ions 32 3.2 Biopanning experiments 33 3.3 Single clone binding studies 38 Discussion 39 4.1 Gallium ions as biopanning target 39 4.2 Phage clone selection 40 Conclusion 44 Acknowledgements 45 CHAPTER III. 46 Author contributions 46 Abstract 47 Introduction 47 Materials and Methods 49 2.1 Handling of phage display library clones 49 2.2 Site-directed mutagenesis experiments 50 2.3 Biosorption experiments 51 Results and Discussion 52 3.1 Experimental context 52 3.2 Original phage clone characterization 53 3.3 Site-directed mutagenesis experiments 56 3.4 Mutant phage clone characterization 57 Conclusions 59 Acknowledgements 60 CHAPTER IV. 61 Author contributions 61 Textual and graphical abstract 62 Introduction 63 Methods 65 2.1 Peptides 65 2.2 Isothermal titration microcalorimetry (ITC) 65 2.3 Preparation of peptide conjugates 65 2.4 Biosorption studies 66 2.5 Model calculation of peptide C3.8 67 Results and Discussion 68 3.1 Interaction studies of free peptides in solution 68 3.2 Biosorption studies with peptide polystyrene conjugates 71 3.2.1 Covalent and site-selective immobilization of peptides 71 3.2.2 Interaction of peptide conjugates with gallium 72 3.2.3 Interaction of peptide conjugates with arsenic 73 3.2.4 Continuous experiments 73 3.3 Model calculation for peptide C3.15 75 Counclusion 76 Acknowledgment 77 CHAPTER V. 78 Obtained insights for the selection of metal-binding peptides in biopanning experiments 79 Conclusions for the development of peptide-based materials for the biosorptive recovery of metal ions from aqueous solutions 81 REFERENCES 85 APPENDIX 94 SUPPORTING INFORMATION FOR CHAPTER IV 94 LIST OF FIGURES 99 LIST OF TABLES 100 LIST OF ABBREVIATIONS 101 LIST OF CHEMICALS 104 ACKNOWLEDGEMENTS 106 CURRICULUM VITAE 109 LIST OF PUBLICATIONS 111

Ce travail de thèse porte sur les propriétés structurales, optiques et électriques de nanostructures et alliages à base de GaP pour la photonique intégrée sur silicium. Parmi les méthodes d’intégration des semi-conducteurs III-V sur Si, l’intérêt de l’approche GaP/Si est tout d’abord discuté. Une étude de la croissance et du dopage de l’AlGaP est présentée afin d’assurer le confinement optique et l’injection électrique dans les structures lasers GaP. Les difficultés d’activation des dopants n sont mises en évidence. Ensuite, les propriétés de photoluminescence des boites quantiques InGaAs/GaP sont étudiées en fonction de la température et de la densité d’excitation. Les transitions optiques mises en jeu sont identifiées comme étant des transitions indirectes de type-I avec les électrons dans les niveaux Xxy et les trous dans les niveaux HH des boites quantiques InGaAs et de type-II avec les électrons dans les niveaux Xz du GaP contraint. Malgré une modification notable de la structure électronique de ces émetteurs, une transition optique directe et type I n’est pas obtenue ce qui reste le verrou majeur pour la promotion d’émetteurs GaP sur Si. La maitrise de l’interface GaP/Si et de l’injection électrique est par ailleurs validée par la démonstration de l’électroluminescence à température ambiante d’une LED GaPN sur Si. Si l’effet laser n’est pas obtenu dans les structures lasers rubans GaP, un possible début de remplissage de la bande Гdans les QDs est discuté. Enfin, l’adéquation des lasers à l’état de l’art avec les critères d’interconnections optiques sur puce est discutée. / This PhD work focuses on the structural, optical, electrical properties of GaP-based nanostructures and alloys for integrated photonics on silicon. Amongst the integration approaches of III-V on Si, the interest of GaP/Si is firstly discussed. A study of the growth and the doping of AlGaP used as laser cladding layers (optical confinement and electrical injection) is presented. The activation complexity of n-dopants is highlighted. Then, the photoluminescence properties of InGaAs/GaP quantum dots are investigated as a function of temperature and optical density. The origin of the optical transitions involved are identified as (i) indirect type-I transition between electrons in Xxy states and holes in HH states of quantum dots InGaAs and (ii) indirect type-II with electrons in Xz states of strained GaP. Despite an effective modification in the electronic structure of these emitters, a direct type I optical transition is not demonstrated. This is the major bottleneck in the promotion of GaP based emitters on Si. This said, the control of the GaP/Si interface and electrical injection are confirmed by the demonstration of electroluminescence at room temperature on Si. If no laser effect is obtained in rib laser architectures, a possible beginning of Г band filling in QDs is discussed. Finally, the adequacy of state of the art integrated lasers with the development of on-chip optical interconnects is discussed.

Les nitrures d’éléments III, à savoir GaN, InN, AlN et leurs alliages, forment une famille de matériaux semi-conducteurs dont les propriétés sont particulièrement intéressantes pour la réalisation de diodes électroluminescentes (LEDs). Leur intérêt réside en particulier dans leur bande interdite qui est directe et qui couvre une large bande spectrale de l’infrarouge (0,65eV pour InN) à l’ultraviolet (6,2eV pour AlN). En raison de l’absence de substrats accordés en maille avec ces matériaux, les couches minces hétéroépitaxiées de nitrure sont généralement touchées par des problèmes de qualité cristalline. Grâce au phénomène de relaxation des contraintes en surface, les nanofils offrent une solution prometteuse pour résoudre ce problème. Ils combinent de nombreux autres avantages : en comparaison des couches minces, l’efficacité quantique interne des LEDs peut être améliorée (surface effective plus importante permettant de diminuer l’effet Auger à courant injecté identique, absence de champ de polarisation en utilisant les facettes non polaires des nanofils) et l’extraction des photons est facilitée par l’effet guide d’onde des nanofils. Cependant, une des difficultés est de parvenir à contrôler la synthèse de ces nano-objets pour garantir une homogénéité des propriétés structurales d’un fil à l’autre et au sein d’un même fil. Dans ce contexte, mon travail de thèse a consisté à étudier d’un point de vue expérimental et théorique l’impact des inhomogénéités structurales sur les propriétés optoélectroniques de dispositifs à nanofils de type LED. J’ai pu mettre en évidence et modéliser un effet de concentration du courant dans les régions riches en indium lorsque les courants injectés sont modérés. Pour de forts courants, le courant se concentre à proximité du contact sur la coquille dopée p. Théoriquement, j’ai montré que la dérive des porteurs de charge dans les puits quantiques et leur diffusion unipolaire et ambipolaire en présence d’un gradient de compositions des puits étaient négligeables. Par ailleurs, je me suis également intéressé à l’interprétation des caractéristiques courant-tension. A l’aide d’un modèle simple, j’ai également identifié la présence de courant de fuite par effet tunnel dans des structures présentant une densité importante de défaut. Dans une seconde partie de ma thèse, je me suis également intéressé à la caractérisation de nanofils à structure coeur-coquille par la technique de courant induit par faisceau d’électrons (Electron Beam Induced Current). La dépendance des cartographies EBIC en fonction de la tension appliquée et de l’énergie du faisceau incident a été modélisée. Ce travail m’a notamment amené à proposer une nouvelle méthode de caractérisation permettant de cartographier les résistivités du coeur et de la coquille des nanofils. / III-nitrides i.e. GaN, InN, AlN and their alloys are semiconductors of choice to fabricate optoelectronic devices such as Light Emitting Diodes (LEDs). One of their most interesting features relies in their direct band gap that covers a very wide spectral range, from infrared (0.65 eV for InN) to UV (6.2 eV for AlN). However, the lack of lattice-matched substrate has been responsible for strong crystalline quality issues in heteroepitaxial thin films. Thanks to stress relaxation at their surface, nanowires provide a smart solution to this problem. Besides, they have a few more assets. In comparison to thin films, nanowires can improve the internal quantum efficiency of LEDs because of their higher effective surface that leads to lowered current densities and thus mitigated Auger effect. The internal quantum efficiency also benefits from the possibility to grow the active region on non polar facets, thus getting rid of the detrimental high internal polarization-induced electric field in quantum wells. Furthermore, the photon extraction efficiency is enhanced by the guiding effect of nanowires. However, despite all this promising advantages, one of the main challenges remains the control of structural homogeneity from wire to wire but also inside single wires.In this context, my work has consisted into studying from an experimental and theoretical point of view the consequences of these structural inhomogeneities on the optoelectronic properties of nanowire based LED devices. I have shown that the current tends to gather into indium-rich regions for moderate bias. At higher bias, the dominant current path though the junction is generally located under the p-contact on the nanowire shell. I have theoretically demonstrated that the unipolar and ambipolar diffusion of carriers as well as their drift induced by a composition gradient inside the quantum wells is not significant in the devices I have studied. Moreover, I took also an interest in the detailed analyze of I-V curves. Thanks to a simple model, I have identified the presence of leakage current related to defect- and phonon-assisted tunneling effect. In the second part of my work, I have focused onto the characterization of core-shell wires using the Electron Beam Induced Current technique. The bias-dependant and acceleration voltage-dependant EBIC maps has been explained with a theoretical model based on equivalent circuits. This study leads me to suggest a new experimental method that can be used to map the nanowire core and shell resistivity.

Ces travaux de thèse portent sur les phénomènes d’amplification du signal de diffusion Raman par effet de surface et par effet de pointe. Des réseaux de motifs métalliques de taille nanométrique arrangés spatialement ont été fabriqués par la méthode de transfert Langmuir-Blodgett et par lithographie à faisceau d’électrons. De telles structures de géométries contrôlées déposées à la surface de lamelles de microscope ont été développées afin d’amplifier le signal Raman de molécules adsorbées par effet SERS (Surface Enhanced Raman Spectroscopy). Ces nanostructures triangulaires en or de taille proche de la longueur d’onde ont des bandes de résonance plasmon dans le domaine spectral visible. En utilisant une source de laser appropriée dans ce domaine spectral, les facteurs d’amplification Raman d’une couche mono-moléculaire d’un dérivé azobenzène sont de plusieurs ordres de grandeur, et ce pour les deux techniques de nano-lithographie employées. Afin de compléter ces premiers résultats, des réseaux de fils d’or avec de grands facteurs de forme ont été fabriqués. Ces derniers montrent des résonances plasmons multipolaires et des facteurs d’amplification de l’ordre de 105. Les techniques de microscopie en champ proche ont également été développées afin de localiser précisément l’exaltation Raman et d’accroitre la résolution spatiale de mesures Raman. Des pointes métalliques en or de taille nanométrique ont ainsi permis d’amplifier localement le signal de diffusion de molécules placées à leur proximité par effet TERS (Tip Enhanced Raman Spectroscopy). Les développements logiciels et mécaniques entre un microscope confocal Raman et un microscope à force atomique ont été implémentés afin de contrôler simultanément les deux instruments. Ce montage expérimental a été appliqué à l’étude de nanofils semi-conducteurs de nitrure de gallium permettant de suivre leur signal vibrationnel avec une résolution spatiale inférieure à 200 nm. / This thesis work focuses on Raman scattering enhancements by metallic nanostructures. In the first part of this work, arrays of metallic patterns with nanometer dimensions were fabricated by the Langmuir-Blodgett deposition technique and electron-beam lithography. Such structures made of gold were fabricated onto microscope slides with the goal to enhance the Raman signal through SERS effect (Surface Enhanced Raman Spectroscopy). These patterns formed by an assembly of triangular nanostructures with sizes of hundreds of nanometers, exhibit plasmon resonance bands in the visible spectral region. By using an appropriate excitation laser source with respect to the plasmon frequency, Raman enhancement factors of a monolayer were found to be of several order of magnitude for both Langmuir-Blodgett and electron-beam lithography platforms. To further complement these results, gold wires arrays with large aspect ratio made by electron-beam lithography showed multipolar plasmon resonances with enhancement factors up to 105. In the second part of this thesis, near-field Raman microscopy has been developed with the aim to localize precisely the Raman enhancement and improve spatial resolution of Raman measurements. Atomic force microscopy gold tips have been used to locally enhance scattering signal of molecules in close proximity to the tip opening new opportunities. This approach known as TERS (Tip Enhanced Raman Spectroscopy) is of significant interest to probe nanomaterials, nanostructures or monolayers. Software and mechanical developments have been made between a confocal Raman microscope and an atomic force microscope to control simultaneously both instruments. This experimental setup was used to characterize gallium nitride semi-conductors nanowires with spatial resolution better than 200 nm.

No description available.

No description available.