Successful operation of Nano-ElectroMechanical Systems (NEMS) critically depends on their working environment and component materials' electromechanical properties. It is equally important that ambient or liquid environment to be seriously considered for NEMS to work as high sensitivity sensors with commercial viabilities. Firstly, to understand interaction between NEMS oscillator and fluid, transfer function of suspended gold nanowire NEMS devices in fluid was calculated. It was found that NEMS's resonance frequency decreased and energy dissipation increased, which constrained its sensitivity. Sensitivity limit of NEMS oscillators was also considered in a statistical framework. Subsequently, suspended gold nanowire NEMS devices were magnetomotively actuated in vacuum and liquid. Secondly, electromechanical properties of gold nanowires were carefully studied and the observed size effect was found to agree with theory, which predicted small changes of electromechanical property compared with bulk gold materials. Finally, it is well recognized that continuous development of new NEMS devices demands novel materials. Mechanical properties of new two-dimensional hexagonal Boron Nitride films with a few atomic layers were studied. Outlook of utilizing ultrathm BN films in next generation NEMS devices was discussed.

One dimensional (1-D) metallic nanostructures (e.g. nanowires, nanorods) have stimulated great interest recently as important building blocks for future nanoscale electronic and electromechanical devices. In this thesis work, gold and nickel nanowires with various diameters were successfully fabricated, and two dedicated platforms, based on (1) a novel micro mechanical device (MMD) assisted with a quantitative nanoindenter and (2) a TEM-AFM sample holder system, were developed and adopted to perform in situ tensile tests inside SEM and TEM on samples with diameter ranging from a few nanometers to hundreds nanometers. Size-dependent mechanical behavior and different fracture mechanisms of gold nanowires had been revealed and discussed. In addition, we discovered cold welding phenomenon for ultrathin gold nanowires (diameter ∠ 10nm), which is anticipated to have potential applications in the future bottom-up integration of metallic 1-D nanostructures and next-generation interconnects for extremely dense logic circuits.

Ground state depletion with individual molecule return (GSDIM) super-resolution microscopy is used to interrogate the location of individual fluorescence bursts from two different nanoparticle-fluorophore systems. The first system consists of fluorophore-labeled DNA molecules on gold nanowire surfaces. In this system carboxytetramethyl rhodamine-labeled double-stranded DNA molecules were bound to the surface of gold nanowires via gold-thiol linkages. The second system focuses on mesoporous silica coated nanorods with dye embedded into the silica coating. The dye molecule, Rhodamine 6G, was incorporated into the silica shell during the nanorod coating procedure. Individual fluorescence bursts were spatially localized using point spread function fitting and used to reconstruct the image of the underlying nanowire or nanorod. / text

DNA origami templates have been studied due the versatility of shapes that can be designed and their compatibility with various materials. This has potential for future electronic applications. This work presents studies performed on the electrical properties of DNA origami templated gold nanowires. Using a DNA origami tile, gold nanowires are site specifically attached in a “C” shape, and with the use of electron beam induced deposition of metal, electrically characterized. These wires are electrically conductive with resistivities as low as 4.24 x 10-5 Ω-m. During moderate temperature processing nanowires formed on DNA origami templates are shown to be affected by the high surface mobility of metal atoms. Annealing studies of DNA origami gold nanowires are conducted, evaluating the effects of atom surface mobility at various temperatures. It is shown that the nanowires separate into individual islands at temperatures as low as 180° C. This work shows that with the use of a polymer template the temperature at which island formation occurs can be raised to 210° C. This could allow for post processing techniques that would otherwise not be possible.

O espalhamento Raman intensificado pela superfície (SERS) é uma importante ferramenta analítica na detecção de moléculas-alvo, portanto a busca por novos substratos SERS que apresentem maiores intensificações e reprodutibilidades espaciais é uma das principais linhas de pesquisa dentro da espectroscopia Raman. Nesta dissertação de mestrado foram obtidos nanotubos de Au (AuNT) através do sputtering (vaporização catódica) sobre uma membrana porosa de policarbonato (PCM) comercial com diâmetros de poro de 50, 100, 200 e 400 nm. Foi verificado um crescimento exponencial dos valores dos fatores de intensificação (EF) com o aumento do diâmetro do poro devido à crescente presença de AuNTs coalescidos, que atuam como hot-spots. Os valores médios de EF variam entre 2,3×103 e 1,2×105, com valor máximo de 2,5×105. Nanotubos e nanofios (AuNF) de Au foram obtidos através da eletrodeposição de Au nas mesmas PCMs utilizando duas densidades de corrente (j): 1,000 e 0,100 mA.cm-2. Nos menores diâmetros de poro foram obtidos AuNFs para j = 1,000 mA.cm-2 e AuNTs para 0,100 mA.cm-2, onde os primeiros apresentaram EF em média 10 vezes superior aos AuNTs de mesmo diâmetro. AuNTs foram obtidos nos maiores diâmetros de poro independentemente de j e apresentando valores de EF similares. Os valores de EF médios variaram entre 2,6×103 e 6,6×105, com valor máximo de 1,5×106. O mesmo crescimento exponencial observado para os AuNTs depositados por sputtering foi observado nestes substratos, decorrente do aumento na quantidade de nanoestruturas coalescidas. Em média seus valores de EF são cerca de 10 vezes superiores aos obtidos nos substratos depositados por sputtering. Todos substratos depositados por sputtering e eletrodepositados tiveram suas ressonâncias plasmônicas de superfície caracterizadas por espectroscopia de absorção no UV-VIS. Substratos tipicamente utilizados na espectroscopia SERS foram sintetizados e utilizados como referência: nanoesferas de Au (AuNS), eletrodo ativado de Au (AuEle) e o substrato comercial Klarite®. Através do emprego de metodologias de cálculo para EF que levassem em conta a geometria de cada sistema foi possível fazer uma comparação direta de todos os substratos. Revelando um desempenho superior dos AuNTs/AuNFs depositados por sputtering ou eletrodepositados frente aos três substrato acima, tanto em termos de magnitude, quanto em termos de reprodutibilidade espacial nos valores calculados para EF. Por fim, foi estudada a variação na frequência e largura a meia altura da banda atribuída ao modo VCC,resp.anel da molécula-prova 4-mercaptopiridina. Foi determinado que a presença de policarbonato residual nos entornos dos AuNTs altera localmente o pH através da modificação do potencial da dupla-camada elétrica. Isto leva ao deslocamento dos equilíbrios de N-protonação e/ou tautomérico da 4-mercaptopiridina em diferentes graus sobre a superfície do substrato. Em concordância com a ausência destes deslocamentos de equilíbrios nos substratos utilizados como referência: AuNS, AuEle e Klarite®, onde o policarbonato não está presente. / The surface enhanced Raman scattering (SERS) is an important analytical tool on the detection of probe-molecules, therefore the search for new SERS substrates which show higher enhancements and spatial reproducibility is one of the main research topics on Raman spectroscopy. In this master thesis Au nanotubes (AuNT) were obtained through the sputtering onto a commercial polycarbonate porous membrane (PCM) with pore diameters of 50, 100, 200 e 400 nm. It was found an exponential growth on the values of the enhancement factor (EF) with the increase of the pore diameter due to an increasing presence of coalesced AuNTs, acting as hot-spots. The average values for EF vary between 2.3×103 and 1.2×105, with maximum value of 2.5×105. Gold nanotubes and nanowires (AuNF) were obtained through the electrodeposition of Au on the same PCMs by using two different current densities (j): 1.000 and 0.100 mA.cm-2. On the smaller pore diameters there were obtained AuNFs for j = 1.000 mA.cm-2 and AuNTs for j = 0.100 mA.cm-2, which the former had shown EF on average 10 times larger the AuNTs with the same diameter. AuNTs were obtained on the larger pore diameters independently of j and having similar values for EF. The average values for EF varied between 2.6×103 and 6.6×105, with maximum value of 1.5×106. The same exponential growth observed for the sputtered AuNTs was observed in these substrates, due to the increase on the quantity of coalesced nanostructures. On average its values for EF are ca. 10 times larger than those obtained for the sputtered substrates. All sputtered and electrodeposited substrates had their surface plasmon resonances characterized by means of UV-VIS absorption spectroscopy. Substrates typically used on SERS spectroscopy were synthetized and used as reference: Au nanospheres (AuNS), roughened Au electrode (AuEle) and the commercial substrate Klarite®. Through employing methodologies for the EF calculation which take into account the geometry of each system it was possible to do a direct comparison among all types of substrates. Revealing an higher performance of the sputtered and/or electrodeposited AuNTs/AuNFs when compared to the three substrates above in terms of both magnitude and spatial reproducibility on the calculated values of EF. Finally, it was studied the variation on the frequency and full width at half maximum of the band assigned to the VCC,ring breathing mode of the 4-mercaptopyridine probe-molecule. It was found that the presence of residual polycarbonate on the AuNTs surroundings locally alters the pH through the modification of the double-layer potential. This leads to the displacement of the N-protonation and/or tautomeric equilibria of the 4-mercaptopyridine in different degrees over the substrate surface. In agreement with the absence of these equilibria displacements on the substrates used as reference: AuNS, AuEle and Klarite®, where the polycarbonate is not present.

O espalhamento Raman intensificado pela superfície (SERS) é uma importante ferramenta analítica na detecção de moléculas-alvo, portanto a busca por novos substratos SERS que apresentem maiores intensificações e reprodutibilidades espaciais é uma das principais linhas de pesquisa dentro da espectroscopia Raman. Nesta dissertação de mestrado foram obtidos nanotubos de Au (AuNT) através do sputtering (vaporização catódica) sobre uma membrana porosa de policarbonato (PCM) comercial com diâmetros de poro de 50, 100, 200 e 400 nm. Foi verificado um crescimento exponencial dos valores dos fatores de intensificação (EF) com o aumento do diâmetro do poro devido à crescente presença de AuNTs coalescidos, que atuam como hot-spots. Os valores médios de EF variam entre 2,3×103 e 1,2×105, com valor máximo de 2,5×105. Nanotubos e nanofios (AuNF) de Au foram obtidos através da eletrodeposição de Au nas mesmas PCMs utilizando duas densidades de corrente (j): 1,000 e 0,100 mA.cm-2. Nos menores diâmetros de poro foram obtidos AuNFs para j = 1,000 mA.cm-2 e AuNTs para 0,100 mA.cm-2, onde os primeiros apresentaram EF em média 10 vezes superior aos AuNTs de mesmo diâmetro. AuNTs foram obtidos nos maiores diâmetros de poro independentemente de j e apresentando valores de EF similares. Os valores de EF médios variaram entre 2,6×103 e 6,6×105, com valor máximo de 1,5×106. O mesmo crescimento exponencial observado para os AuNTs depositados por sputtering foi observado nestes substratos, decorrente do aumento na quantidade de nanoestruturas coalescidas. Em média seus valores de EF são cerca de 10 vezes superiores aos obtidos nos substratos depositados por sputtering. Todos substratos depositados por sputtering e eletrodepositados tiveram suas ressonâncias plasmônicas de superfície caracterizadas por espectroscopia de absorção no UV-VIS. Substratos tipicamente utilizados na espectroscopia SERS foram sintetizados e utilizados como referência: nanoesferas de Au (AuNS), eletrodo ativado de Au (AuEle) e o substrato comercial Klarite®. Através do emprego de metodologias de cálculo para EF que levassem em conta a geometria de cada sistema foi possível fazer uma comparação direta de todos os substratos. Revelando um desempenho superior dos AuNTs/AuNFs depositados por sputtering ou eletrodepositados frente aos três substrato acima, tanto em termos de magnitude, quanto em termos de reprodutibilidade espacial nos valores calculados para EF. Por fim, foi estudada a variação na frequência e largura a meia altura da banda atribuída ao modo VCC,resp.anel da molécula-prova 4-mercaptopiridina. Foi determinado que a presença de policarbonato residual nos entornos dos AuNTs altera localmente o pH através da modificação do potencial da dupla-camada elétrica. Isto leva ao deslocamento dos equilíbrios de N-protonação e/ou tautomérico da 4-mercaptopiridina em diferentes graus sobre a superfície do substrato. Em concordância com a ausência destes deslocamentos de equilíbrios nos substratos utilizados como referência: AuNS, AuEle e Klarite®, onde o policarbonato não está presente. / The surface enhanced Raman scattering (SERS) is an important analytical tool on the detection of probe-molecules, therefore the search for new SERS substrates which show higher enhancements and spatial reproducibility is one of the main research topics on Raman spectroscopy. In this master thesis Au nanotubes (AuNT) were obtained through the sputtering onto a commercial polycarbonate porous membrane (PCM) with pore diameters of 50, 100, 200 e 400 nm. It was found an exponential growth on the values of the enhancement factor (EF) with the increase of the pore diameter due to an increasing presence of coalesced AuNTs, acting as hot-spots. The average values for EF vary between 2.3×103 and 1.2×105, with maximum value of 2.5×105. Gold nanotubes and nanowires (AuNF) were obtained through the electrodeposition of Au on the same PCMs by using two different current densities (j): 1.000 and 0.100 mA.cm-2. On the smaller pore diameters there were obtained AuNFs for j = 1.000 mA.cm-2 and AuNTs for j = 0.100 mA.cm-2, which the former had shown EF on average 10 times larger the AuNTs with the same diameter. AuNTs were obtained on the larger pore diameters independently of j and having similar values for EF. The average values for EF varied between 2.6×103 and 6.6×105, with maximum value of 1.5×106. The same exponential growth observed for the sputtered AuNTs was observed in these substrates, due to the increase on the quantity of coalesced nanostructures. On average its values for EF are ca. 10 times larger than those obtained for the sputtered substrates. All sputtered and electrodeposited substrates had their surface plasmon resonances characterized by means of UV-VIS absorption spectroscopy. Substrates typically used on SERS spectroscopy were synthetized and used as reference: Au nanospheres (AuNS), roughened Au electrode (AuEle) and the commercial substrate Klarite®. Through employing methodologies for the EF calculation which take into account the geometry of each system it was possible to do a direct comparison among all types of substrates. Revealing an higher performance of the sputtered and/or electrodeposited AuNTs/AuNFs when compared to the three substrates above in terms of both magnitude and spatial reproducibility on the calculated values of EF. Finally, it was studied the variation on the frequency and full width at half maximum of the band assigned to the VCC,ring breathing mode of the 4-mercaptopyridine probe-molecule. It was found that the presence of residual polycarbonate on the AuNTs surroundings locally alters the pH through the modification of the double-layer potential. This leads to the displacement of the N-protonation and/or tautomeric equilibria of the 4-mercaptopyridine in different degrees over the substrate surface. In agreement with the absence of these equilibria displacements on the substrates used as reference: AuNS, AuEle and Klarite®, where the polycarbonate is not present.

Thesis (Ph.D. (Physics)) --University of Limpopo, 2011 / The importance of gold for scientific uses is of fundamental importance to research and technology developments. The bulk gold shows reluctance to participate in chemical reactions, the effect which has been corrected by the change in the size towards nanoclusters. It is therefore imperative that the structure of gold nanomaterials is understood for better applications in catalysis and other developments. Molecular dynamics and the density functional theory have proven to be good tools in computational material science and have thus been used to greater lengths. Molecular dynamics simulations on different gold nanoclusters and nanotubes were successfully carried out at different thermodynamic conditions. The effect of size on the melting of materials was duly tested and our results to some extend agree with what has already been reported. Gold nanoclusters show melting below the bulk and the melting temperatures increase with cluster size. However, the Au55 cluster shows different results in that it melts above the bulk due to structural reconstruction. The structure of the clusters changes from spherical shapes to tetragonal or face centred cubic (fcc) structures. Gold nanotubes show no resistance to temperature and different configurations are obtained in different ensembles. Single wall nanotubes form spherical clusters in the NVT while the NPT conditions give patches of clusters at elevated temperatures. The multi wall nanotubes also form spherical clusters in the NVT but fcc structures are obtained in the NPT Berendsen ensemble towards melting. Ab initio calculations in DMOL3 code on different gold nanoclusters show the stability of the clusters to increase with size and the Au3 and Au8 clusters contain the most stable structures. The Au-Au bond length in the dimer was obtained to within reasonable agreement with experiments and other theoretical works. Doping of the clusters further improved their stability although different impurities give different observations. The QMERA code calculations show that a gold atom on top of the surface causes slanting of the outer MD layers. The morphology of the quantum atoms also changes as compared to the neutral surface and the results are compared by the DMOL3 code which confirms the QMERA results. / Mintek, and the National Research Foundation

L'objectif principal de ce travail est d'étudier les propriétés d'un composite polymère-métal d'un point de vue physique, thermique, mécanique et électrique large bande. Pour cela, des fils d'or à haut facteur de forme (190) ont été élaborés par un procédé d'électrodéposition dans un template. Les fils submicroniques d'or ont été dispersés dans une matrice polymère PVDF pour l'élaboration des composites conducteurs faiblement chargés. Le comportement électrique des composites met en évidence le phénomène de la percolation électrique, avec un seuil de 1,33 %vol. La dispersion des fils submicroniques d'or au sein de la matrice PVDF est homogène, avec une légère orientation. L'analyse mécanique permet de mettre en évidence le rôle de renfort des fils d'or dans la matrice PVDF et l'influence des fils sur la structure physique du PVDF. Cela se traduit par une rigidification de la matrice PVDF et plus particulièrement l'effet sur la relaxation ac , associée à l'interface cristallite-phase amorphe du PVDF. L'étude de la conductivité statique et dynamique en basse (10-2 à 106 Hz) et haute (106 à 109 Hz) fréquence montre un changement de régime de transport de charge avec une activation thermique. La conduction par tunneling est prédominante à basse température, tandis que la conductivité au-delà est expliquée par les modèles d'Efros et Shklovskii et le modèle de saut de barrières corrélés (CBH), respectivement pour la partie statique et dynamique. Les paramètres déterminés avec les modèles présentent une bonne corrélation avec les propriétés mécaniques, ce qui permet d'améliorer la compréhension des phénomènes de transport de charge dans des systèmes hétérogènes tels les composites polymère-métal faiblement chargés. / The aim of this work is to study the properties of a polymer-metal composite, with regards to physical, thermal, mechanical and broad band electrical analyses. High aspect ratio gold nanowires (Au NW) were prepared using a template electrodeposition method (aspect ratio of 190 determined by image analysis). The gold nanowires were dispersed in a PVDF polymer matrix to form low-filled conducting composites. The electrical conductivity of the composites exhibit electrical percolation behaviour with a critical volume fraction of 1.33%. SEM images show a slightly oriented but homogenous dispersion of AU NWs within the PVDF matrix. Mechanical analysis confirms that the homogenous dispersion Au NWs reinforces the PVDF matrix and highlights the influence of Au NWs on the physical structure of the PVDF matrix. This is confirmed by an increase in G' values and more specifically the ac relaxation process (associated with the crystallite-amorphous phase interface). Analysis of static and dynamic conductivity for low (10-2 to 106 Hz) and high frequency (106 to 109 Hz) regions reveals a thermally-activated charge transport process: tunneling being the predominant mechanism at low temperatures, the Efros and Shklovskii (ES) and Correlated Barrier Hopping (CBH) models being responsible for static and dynamic conductivity, respectively. The models were found to be coherent with the structure and mechanical properties of the composites, leading to a better understanding of charge transport mechanisms in low-filled polymer-metal composites.

Orientador: Edison Zacarias da Silva / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Fisica Gleb Wataghin / Made available in DSpace on 2018-08-22T13:09:46Z (GMT). No. of bitstreams: 1 Nascimento_AnaPaulaFavaro_D.pdf: 24653202 bytes, checksum: cb09f1eecbbf100b37ad50fd3a26f857 (MD5) Previous issue date: 2013 / Resumo: A fabricação e o estudo de nanofios de ouro despertam grande interesse na comunidade científica, na tentativa de maior entendimento de efeitos quânticos de sistemas em escala reduzida, assim como na possibilidade de seu uso em aplicações tecnológicas. Uma vez que os nanofios de ouro apresentam propriedades surpreendentes quando dopados por impurezas atômicas fomos motivados a estudar como estas se formam. Devido ao fato de em escala nanoscópica o ouro apresentar atividade catalítica, consideramos que a presença de impurezas se deve a reação de pequenas moléculas em nanofios de Au. O estudo foi realizado por meio de cálculos abinitio via Teoria do Funcional da Densidade, usando o código computacional SIESTA. A metodologia para o estudo da estrutura eletrônica desses sistemas foi a de otimização de geometria e de dinâmica molecular ab initio. Nosso foco de estudo foi encontrar caminhos reacionais para a formação de impurezas atômicas de carbono ou de oxigênio nas cadeias atômicas lineares de nanofios monoatômicos. A análise se baseou na interação entre duas moléculas catalisada pelo nanofio, as moléculas consideradas em nosso estudo foram CO e O2. Um estudo extensivo e detalhado das possíveis reações foi feito. Dentre os vários caminhos estudados, uma reação sequencial onde uma molécula de O2 é adsorvida por apenas um dos seus oxigênios, inicia um processo, que seguido pela adsorção de uma molécula de CO, leva a formação de um complexo O2-CO ligado a cadeia atômica do nanofio. Nós mostramos situações onde este complexo fica ativado e reage formando uma molécula de CO2 que vai para a fase gasosa deixando o nanofio dopado com um átomo de oxigênio. Portanto este trabalho apresenta um caminho reacional para a formação de uma impureza atômica na cadeia atômica de um nanofio de ouro, uma questão que esperava uma solução a quase uma década. / Abstract: The manufacture and the study of gold nanowires weakened great interest of the scientific community in the quest for better understanding of the quantum effects in systems with reduced scales and also due to the possibility of their use in technological applications. Since gold nanowires present novel and surprising properties when doped with atomic impurities, this led us into the search to understand how these impurities can be produced. Due to the fact that gold in nanoscale presents catalytic activity, we considered the possibility of chemical reactions with small molecules in the presence of gold nanowires. The present study was performed with ab initio calculations based in the density functional theory as implemented by the SIESTA code. The methodology for the electronic structure studies was the geometry optimization using conjugated gradient method and abinitio molecular dynamics. Our focus was to find reaction paths to produce atomic impurities of carbon and oxygen in linear atomic chains of gold nanowires. The analysis was based in the reaction of two molecules catalized by the nanowire, the molecules considered in this study were CO and O2. An extensive and detailed study of possible pathways was undertaken. Among the various paths, a sequential reaction where only one O of a adsorbed O2 molecule attached to the nanowire, started the process, followed by the adsorption of a CO molecule nearby that formed an O2-CO complex attached to the atomic chain of the nanowire. We presented circumstances in which this complex becomes activated and evolves to form a CO2 molecule that goes into the gas phase leaving an atomic oxygen impurity attached to the linear chain. Therefore, this work presented a reactional path to the formation of an atomic impurity in the atomic chain of a gold nanowire, a question that waited an answer for almost ten years. / Doutorado / Física / Doutora em Ciências

Ce travail concerne le développement d’un nouveau type de microscopie optique en champ proche (SNOM) basé sur la mise en œuvre de sondes dite actives qui utilisent le signal de génération de seconde harmonique (SHG) d’un petit nombre de molécules orientées. L’orientation de ces molécules est obtenue par l’application d’un champ électrique statique dans une jonction constituée d’une pointe métallique effilée placée à proximité d’un substrat conducteur et immergée dans une solution de molécules dipolaires non-linéaires. L’excitation laser de ces molécules localement orientées permet d’obtenir une polarisation non-lineaire à fréquence double qui constitue une nanosource de lumière intrinsèquement localisée et pouvant interagir avec le champ proche du substrat. Nous nous sommes intéressés à l’imagerie de nano-objets lithographiés par cette technique de SNOM-SHG. Nous avons pu démontrer la possibilité d’obtenir une résolution de l’ordre de 200 nm, soit une résolution meilleure d’un facteur 2 par rapport à la limite de diffraction.Nous avons ensuite étudié les moyens d’optimiser les performances de ce nouveau type de sondes SNOM-SHG. Une voie consiste à exploiter les propriétés d’antenne optique de pointes métalliques effilées, qui peuvent être le siège d’effets d’exaltation du champ électromagnétique résultant de la singularité géométrique de ces objets (extrémité effilée) ou de l’excitation de résonances plasmons. Afin de pouvoir quantifier ces effets, nous avons entrepris la caractérisation, par luminescence à 2 photons (TPL), de nanofils d’or considérés comme objets de référence pour mimer une pointe. Des fils lithographiés ainsi que des fils issus de chimie colloïdale ont été étudiés de façon à mieux comprendre à la fois l’influence de la forme et de la cristallinité des objets sur les exaltations de champ. Des études simultanées de la géométrie et des propriétés optiques d'un nanofil unique ont été menées au moyen d'un microscope optique inversé associé à une excitation laser et couplé à un microscope à force atomique (AFM) dont la pointe est préalablement réglée pour coïncider avec le spot laser. En balayant l’échantillon, nous pouvons directement confronter l’image topographique de l’objet à la cartographie de points chauds enregistrés à sa surface, le signal de TPL étant directement corrélé à la densité locale d’états électromagnétiques. Nous avons pu montrer que les fils lithographiés et les fils colloïdaux présentaient des facteurs d’exaltation locale de champ différents, la cristallinité des objets pouvant aussi être révélée que via l’analyse spectrale du signal de TPL émis. Enfin, un dernier volet important de mon travail a consisté à faire évoluer le banc expérimental précédemment développé au laboratoire de façon à pouvoir réaliser simultanément des caractérisations de type SNOM-SHG et des caractérisations topographiques. Dans ce but, nous avons travaillé à l’intégration d’une tête AFM diapason sur notre banc de microscopie non-linéaire. Au-delà des aspects électroniques liés à l’optimisation du fonctionnement de ce diapason, le couplage du faisceau laser dans le microscope a également été entièrement reconfiguré. / This work deals with the development of a new kind of scanning near-field optical microscopy (SNOM) based on the realization of so-called active probes taking advantage of the second harmonic generation (SHG) signal coming from a few oriented molecules. The orientation of these molecules is obtained by applying a static electric field in a junction made of a sharp metallic tip placed close to a conductive substrate and immersed in a solution containing dipolar non-linear molecules. A second order nonlinear polarization is obtained from these locally oriented molecules following their excitation with a laser beam finally leading to a nanosource of light intrinsically localized and able to interact with the near-field of the substrate.We have investigated this SNOM-SHG technique to image nano-objects made by e-beam lithography. We were able to demonstrate that a resolution of about 100 nm could be reached, which appears better (of a factor2) than the diffraction limit.We have then been focusing on the way to improve the capabilities of this new type of SNOM-SHG probes. One approach consists in taking advantage of the optical antenna effects that can occur at the end of sharp tips, where the electromagnetic field can be enhanced due to geometrical effects (sharp extremities) or due to the excitation of plasmon resonances. In order to quantify these field enhancements, we have carried out the characterization of gold nanowires using two-photon luminescence (TPL) ; considering these wires as reference objects that can mimic tips. Nanowires made by e-beam lithography and nanowires synthesized by colloidal chemistry have both been studied in order to have a better understanding of the influence of the shape and the crystallinity on the field enhancements. Simultaneous analysis of the geometry and the optical properties of a single nanowire has been carried out using an inverted microscope associated to a laser excitation and coupled to an atomic force microscopy (AFM) which tip is previously aligned with the laser spot. When scanning the sample, we can directly correlate the topographic image of the object to the mapping of the hotspots recorded on its surface, the TPL signal being directly linked to the electromagnetic local density of states. We were able to evidence that both nanowires made by e-beam lithography or synthesized by colloidal chemistry exhibit different field enhancement factors, the crystallinity of the objects being also revealed following the spectral analysis of the emitted TPL signal.Finally, a last important part of my work has dealt with the evolution of the experimental setup previously developed in the laboratory in order to be able to achieve simultaneously SNOM-SHG type and topographic characterizations. We have therefore been working on the integration of an AFM tuning fork head to our nonlinear optical bench. Above the electronic aspects related on the optimization of the tuning fork implementation, the coupling of the laser beam in the microscope has also been reconfigured.