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In this work, we use optical methods to study electrochemical reactions and processes occurring on the nanometer length scale. Optical methods are advantageous over traditional electrochemical methods because of their high spatial resolution and sensitivity at both the single nanoparticle and single molecule level. This dissertation describes a series of studies in which super-localization and dark-field optical imaging is used to provide insight into spatial and temporal heterogeneity in nanoscale electrochemical systems with <25 nm spatial resolution. In the first set of experiments, three-dimensional (3-D) super-resolution imaging is used to determine the tip-substrate distance in nanoscale scanning electrochemical microscopy (SECM) with precision better than 25 nm. Correlating the tip-substrate distance using both optical and electrochemical techniques showed excellent agreement. Second, single nanoparticles (NP) were delivered through a nanopipette, and their resistive-pulse signals were correlated with a fluorescence optical signal. The diffusion trajectories of individual NP delivered to the external solution and to an electrified interface were obtained by 3-D super-resolution imaging, and showed signatures of both sub-diffusive and super-diffusive behavior, depending on the balance of forces between the flow from the pipette and the applied potential at the electrified substrate. Next, we studied the influence of surface oxide layers on single silver NP electrodissolution by tracking the intensity and spatial variation of scattering from single nanoparticles over time. We discovered that silver NPs can undergo electrodissolution in either a spatially symmetric or asymmetric manner, based on the nature of the surface oxide layer. Moreover, we also reported the simultaneous electrodeposition of silver oxide at the electrode surface during the electrodissolution of silver NPs, which enabled us to study the effect of multiple simultaneous redox reactions and their effects on one another. Overall, these experiments reveal local heterogeneity in nanoscale electrochemical processes and allow for many single nanoparticles to be measured in parallel, revealing relationships that are hidden using traditional electrochemical measurements. / Chemistry

Choque séptico é caracterizado por desequilíbrio entre o transporte e o consumo de oxigênio, podendo acarretar hipóxia tecidual. A disfunção microcirculatória, característica cardinal da fisiopatologia do choque séptico, causa má distribuição de fluxo sanguíneo microvascular e, consequentemente, shunt de oxigênio, disóxia tissular e, teoricamente, diminuição no consumo de oxigênio (VO2) pela célula. No presente estudo, foi investigada a associação entre alterações microcirculatórias causadas pela sepse e o consumo de oxigênio em pacientes pediátricos. Dezessete crianças com choque séptico ressuscitadas foram estudadas em quatro momentos durante a internação na unidade de terapia intensiva (dentro de 24, 48 e 72 horas após a admissão ou diagnóstico de choque e após a resolução deste, antes da extubação traqueal). A microcirculação sublingual foi avaliada utilizando o método de imagem Sidestream dark field (SDF) e o VO2 foi calculado através da calorimetria indireta. Outras variáveis hemodinâmicas, como transporte de oxigênio, índice cardíaco, pressão arterial invasiva, lactato arterial e saturação venosa central, foram coletadas. Embora as variáveis hemodinâmicas tenham se mantido em níveis satisfatórios, graves alterações na microcirculação foram visualizadas, especialmente na densidade de vasos pequenos perfundidos (DVPP), na proporção de vasos pequenos perfundidos (PVPP) e no índice de fluxo microvascular (MFI). Foram encontradas assosciações significativas entre o VO2 e os parâmetros da microcirculação: dVO2 e dDVPP (&#946; coefficient= 6,875; p<0,001), dVO2 e dPVPP (&#946; coefficient=92,246; p<0,001) e dVO2 e dMFI (&#946; coefficient=21,213; p<0,001). Não foram encontradas correlações entre as alterações microcirculatórias e as outras variáveis. Em conclusão, este estudo mostrou que pacientes pediátricos com choque séptico apresentaram grave disfunção microvascular e que o fluxo microcirculatório alterado estava associado ao VO2, podendo estar implicado na fisiopatologia da disóxia tecidual da sepse. / Septic shock is characterized by the imbalance between oxygen delivery and consumption leading to tissue hypoxia. Microcirculatory dysfunction, a key element of septic shock pathogenesis, elicits maldistribution of microvascular blood flow and consenquently oxygen shunt, tissue oxygenation debt and, theoretically, impaired oxygen consumption (VO2). In this study, it was investigated if there is an association between microcirculatory changes and VO2 in pediatric patients with septic shock. Seventeen resuscitated patients with septic shock were studied in four moments (within 24hr, 48hr and 72hr of the admission or diagnosis of shock and after its resolution, prior to extubation). Sublingual microcirculation was evaluated using Sidestream dark field (SDF) imaging and VO2 was measured directly by indirect calorimetry. Other hemodynamic variables, like cardiac index, oxygen delivery, invasive arterial pressure, arterial lactate and central venous oxygen saturation were also recorded. Although global hemodynamic variables were within satisfactory ranges, microvascular variables were markedly altered, especially microvascular flow index (MFI), proportion of perfused small vessels (PPV) and perfused small vessel density (PVD). Significant associations between oxygen consumption and microcirculatory parameters were found: dVO2 and dPVD (&#946; coefficient= 6.875; p<0.001), dVO2 and dPPV (&#946; coefficient=92.246; p<0.001) and dVO2 and dMFI (&#946; coefficient=21.213; p<0.001). There was no correlation between microcirculatory alterations and other variables in this study. In conclusion, this study showed that pediatric patients with septic shock presented severe microcirculatory dysfunction and abnormal microvascular blood flow could be associated to oxygen consumption.

Choque séptico é caracterizado por desequilíbrio entre o transporte e o consumo de oxigênio, podendo acarretar hipóxia tecidual. A disfunção microcirculatória, característica cardinal da fisiopatologia do choque séptico, causa má distribuição de fluxo sanguíneo microvascular e, consequentemente, shunt de oxigênio, disóxia tissular e, teoricamente, diminuição no consumo de oxigênio (VO2) pela célula. No presente estudo, foi investigada a associação entre alterações microcirculatórias causadas pela sepse e o consumo de oxigênio em pacientes pediátricos. Dezessete crianças com choque séptico ressuscitadas foram estudadas em quatro momentos durante a internação na unidade de terapia intensiva (dentro de 24, 48 e 72 horas após a admissão ou diagnóstico de choque e após a resolução deste, antes da extubação traqueal). A microcirculação sublingual foi avaliada utilizando o método de imagem Sidestream dark field (SDF) e o VO2 foi calculado através da calorimetria indireta. Outras variáveis hemodinâmicas, como transporte de oxigênio, índice cardíaco, pressão arterial invasiva, lactato arterial e saturação venosa central, foram coletadas. Embora as variáveis hemodinâmicas tenham se mantido em níveis satisfatórios, graves alterações na microcirculação foram visualizadas, especialmente na densidade de vasos pequenos perfundidos (DVPP), na proporção de vasos pequenos perfundidos (PVPP) e no índice de fluxo microvascular (MFI). Foram encontradas assosciações significativas entre o VO2 e os parâmetros da microcirculação: dVO2 e dDVPP (&#946; coefficient= 6,875; p<0,001), dVO2 e dPVPP (&#946; coefficient=92,246; p<0,001) e dVO2 e dMFI (&#946; coefficient=21,213; p<0,001). Não foram encontradas correlações entre as alterações microcirculatórias e as outras variáveis. Em conclusão, este estudo mostrou que pacientes pediátricos com choque séptico apresentaram grave disfunção microvascular e que o fluxo microcirculatório alterado estava associado ao VO2, podendo estar implicado na fisiopatologia da disóxia tecidual da sepse. / Septic shock is characterized by the imbalance between oxygen delivery and consumption leading to tissue hypoxia. Microcirculatory dysfunction, a key element of septic shock pathogenesis, elicits maldistribution of microvascular blood flow and consenquently oxygen shunt, tissue oxygenation debt and, theoretically, impaired oxygen consumption (VO2). In this study, it was investigated if there is an association between microcirculatory changes and VO2 in pediatric patients with septic shock. Seventeen resuscitated patients with septic shock were studied in four moments (within 24hr, 48hr and 72hr of the admission or diagnosis of shock and after its resolution, prior to extubation). Sublingual microcirculation was evaluated using Sidestream dark field (SDF) imaging and VO2 was measured directly by indirect calorimetry. Other hemodynamic variables, like cardiac index, oxygen delivery, invasive arterial pressure, arterial lactate and central venous oxygen saturation were also recorded. Although global hemodynamic variables were within satisfactory ranges, microvascular variables were markedly altered, especially microvascular flow index (MFI), proportion of perfused small vessels (PPV) and perfused small vessel density (PVD). Significant associations between oxygen consumption and microcirculatory parameters were found: dVO2 and dPVD (&#946; coefficient= 6.875; p<0.001), dVO2 and dPPV (&#946; coefficient=92.246; p<0.001) and dVO2 and dMFI (&#946; coefficient=21.213; p<0.001). There was no correlation between microcirculatory alterations and other variables in this study. In conclusion, this study showed that pediatric patients with septic shock presented severe microcirculatory dysfunction and abnormal microvascular blood flow could be associated to oxygen consumption.

Using current technology, it is now possible to probe material at atomic length scales, increasing our fundamental understanding of material behavior and properties. Metastable β titanium alloys are a subset of titanium alloys with huge potential for the aerospace sector. However, they exhibit atomic transformations which, even after 60 years of research, are still disputed. For example, these alloys are strengthened using the ω phase, but the mechanism by which this phase forms and its stability are still in question. The aim of this PhD project was to investigate the strengthening of metastable Ti-15wt.%Mo by understanding the stability and transformation pathways which make the metastable β titanium alloy class unique. Athermal ω shares the same composition as the β matrix and is formed by rapid cooling from the β phase field. The classical theory of athermal ω formation is based upon a diffusion-less mechanism in which consecutive pairs of {111}β planes collapse together. However, latest high-resolution electron microscope observations have suggested chemical alterations occur as well, which give reason to challenge this classical formation mechanism. Two novel methods were explored to determine the nature of the ω phase: 1) electron imaging of thin material at different collection angles and 2) total X-ray scattering analysis of large volumes of material. Complementary techniques are invaluable since thin foil artefacts were identified. In particular, a new B2 structured phase in the Ti-15wt.%Mo alloy was observed only in thin electron transparent material. Experimental data from the two new methods were compared to simulations. It was found that a frozen phonon description of the ω structure provided a best fit in both scenarios. The results are therefore consistent with the classical theory of ω formation but the collapse of the {111}β planes towards the ω phase is not considered complete.

Longtemps considérées comme néfastes, les contraintes sont devenues un des moyens principaux pour améliorer les performances des dispositifs métal-oxyde-semiconducteur (MOS). En effet, les déformations générées augmentent sensiblement la mobilité des porteurs dans le silicium. C'est dans ce cadre que j'ai étudié, par holographie électronique en champ sombre (DFEH), les déformations cristallines engendrées par certaines étapes clés du procédé de fabrication de transistors planaires de dernière génération, totalement déplétés car réalisés sur des substrats silicium sur isolant (FD-SOI). La DFEH est une technique de microscopie électronique en transmission (TEM), récemment inventée au CEMES, qui permet de cartographier les déformations cristallines avec une résolution spatiale nanométrique et une précision de 10-4 sur des champs de vue micrométriques. J'ai mis au point et utilisé des modélisations par éléments finis afin de comprendre puis reproduire mes résultats expérimentaux et ainsi identifier les phénomènes mécaniques mis en jeu au cours de différentes étapes. Après avoir prouvé que la DFEH est adaptée à la mesure des champs de déformation dans les structures MOS FDSOI (couche superficielle de Si désorientée vis-à-vis du substrat de référence), je me suis intéressé au procédé de conversion de films minces de Si en SiGe, par la méthode dite de "condensation de germanium". J'ai montré que cette technique permet d'obtenir des films minces de type SiGe (SGOI) pseudomorphes, de composition variable. Les déformations hors plan mesurées par DFEH mettent en évidence les deux mécanismes affectant la redistribution du Ge (diffusion et injection), dont l'importance relative dépend de la température à laquelle s'effectue le procédé. De plus, j'ai montré que ces films minces SGOI, initialement contraints, se relaxaient très fortement lors de leur gravure en vue de la fabrication de substrats co-intégrés SOI/SGOI. J'ai pu identifier que cet effet, initialement observé à partir de mesures électriques et connu sous le nom d'effet "SA/SB", ne pouvait être dû qu'à des caractéristiques mécaniques dégradées de l'interface SiGe/SiO2. Je me suis ensuite intéressé à certaines des étapes clés de la fabrication du transistor suspectées de modifier l'état de déformation de la structure, telles que la fabrication de l'empilement de grille et des sources/drains ainsi que de la siliciuration nécessaire à la prise des contacts. J'ai pu expliquer en quoi et pourquoi ces étapes impactaient l'état final de déformation du canal du transistor et donc ses performances. Par ailleurs, je montre comment et dans quelles limites la DFEH peut être utilisée pour mesurer des concentrations de dopants, en conservant une résolution nanométrique. J'ai particulièrement étudié le cas (favorable) du bore dans le silicium et, après couplage à des mesures électriques, j'ai ainsi pu calculer le coefficient reliant les déformations mesurées aux concentrations de bore en substitution. Finalement, j'ai comparé et discuté des différences entre informations fournies par DFEH et par diffraction de rayons X haute résolution. Une annexe complète ce travail et discute des conditions optiques et d'utilisation optimales des sources à émission de champ Schottky équipant un TEM, notamment de la contribution des lobes d'émission latérale sur le degré de cohérence de la sonde. / After being considered harmful for a long time, stress became one of the principal means to improve metal-oxide-semiconductor (MOS) device performance. Indeed, the generated strains significantly increase carrier mobility in silicon. Within this context, I used dark-field electron holography (DFEH) to study the crystalline strains generated by some key steps of the manufacturing process of latest generation of planar transistors, fully depleted as produced on silicon on insulator substrates (FD-SOI). DFEH is a transmission electron microscopy (TEM) technique, recently invented at CEMES, which allows crystalline strain to be mapped with nanometric resolution and an accuracy of 10-4 over micrometric fields of view. I developed and used finite element models in order to understand, then reproduce, my experimental results and thus identify the mechanical phenomena involved during different processing steps. After proving that DFEH is suitable for strain fields mapping in FDSOI MOS structures (Si surface layer disorientated in respect of the reference substrate), I have been interested in the conversion process of thin Si films into SiGe, by a method known as "germanium condensation". I showed that this technique enables pseudomorphous thin SiGe films (SGOI) of variable composition to be obtained. The out-of-plane strain measured by DFEH emphasises the two mechanisms affecting the Ge redistribution (diffusion and injection), whose relative importance depends on the temperature of the process. Moreover, I showed that these thin SGOI films, initially stressed, relax strongly during the etching carried out to manufacture co-integrated SOI/SGOI substrates. I could identify that this effect, initially observed by electrical measurements and known as "SA/SB" effect, can only be explained by a degradation of the mechanical characteristics of the SiGe/SiO2 interface. I have also been interested in some of the key steps of the transistor manufacturing suspected to modify the structural strain state, such as the grid stack and sources/drains processes, as well as salicidation necessary to form the contacts. I was able to explain how and why these steps impact the final strain state of the transistor channel and thus its performance. In a separate development, I have shown how DFEH can be used to measure doping concentrations while preserving a nanometric resolution, and discuss its limits. I studied in particular the (favourable) case of boron doping in silicon and, after electrical measurements coupling, I calculated the coefficient connecting the measured strains to the boron substitution concentrations. Finally, I compared and discussed the differences between information obtained by DFEH and high resolution X-ray diffraction. An appendix completes this work and discusses the optical and optimal use conditions of Schottky field emission sources equipping a TEM, in particular the contribution of side-emission lobes on the degree of coherence of the probe.

Cette thèse porte d'une part sur l'étude de la stabilité du biexciton dans le nanotube de carbone et, d'autre part, sur le contrôle de l'émission du nanotube par le couplage des nanotubes de carbone à des antennes plasmoniques. La technique de spectroscopie optique non-linéaire de saturation d'absorption, appliquée aux nanotubes de carbone, nous a permis d'effectuer la première observation du biexciton dans cette nanostructure. Plus précisément, deux raies d'absorptions induites sont observées et attribuées au trion et à l'exciton par des études en températures et en puissance du laser de pompe. La mise en oeuvre d'une configuration à trois faisceaux basée sur un schéma en double-pompe permet de confirmer la photo-génération du biexciton en tant qu'excitation élémentaire du nanotube de carbone. Le biexciton est observé avec une énergie de liaison de 107 ± 1 meV pour la chiralité (9,7) et présente un profil asymétrique de Fano. Une première estimation de la dynamique de recombinaisondu biexciton est donnée par description quantitative du processus de Fano. Le modèle est basé sur le formalisme de la susceptibilité non-linéaire du troisième ordre χ(3) incluant le couplage coulombien entre le biexciton et le continuum des paires électron-trou de la première singularité de Van Hove. Le facteur de Fano est évaluée à q = 5 et conduit à l'estimation du taux de recombinaison Auger du biexciton B ∈ [0.1; 1] μm·ps−1 . Le rendement radiatif du biexciton est ainsi estimé à 10−6 .Dans le but d'étudier les nanotubes en cavité plasmonique, une expérience de micro-photoluminescence et une expérience de spectroscopie en champ sombre, sont développés dans le domaine spectrale des télécommunications (1.3 μm et 1.55 μm). La caractérisation de divers types échantillons de nanotube et des antennes plasmoniques sont présentés. Des résultats préliminaires sur un échantillon de nanotubes associés dans une configuration patch à des antennes plasmoniques montrent une corrélation entre la position des antennes et les zones luminescentes, ainsi qu'un changement de l'allure des spectres de photoluminescence. Ces premiers résultats constituent une transition dans la démarche de notre projet. L'étape de calibration des expériences est en phase de finition et l'étude des propriétés physique des nanotubes en cavité plasmonique représente désormais une activité opérationnelle au sein de notre équipe. / This thesis focus on both the biexciton's stability in carbon nanotubes, and the control of the nanotube emission through its coupling to plasmonic antenna.We report the first observation of biexciton in carbon nanotubes by means of spectral holeburning nonlinear optical spectroscopy. More precisely, two induced absorption lines are detected and assigned to trion and biexciton after investigation of their temperature and pump power dependences. An additional proof of the detection of the biexciton, as an elementary excitation of carbonnanotubes, is given in a three-beam configuration based on a two-pump scheme. The biexciton of the (9,7) chirality is observed with a binding energy of 107 ± 1 meV and shows an asymetric Fano lineshape. A first estimation of the biexciton's recombinaison dynamics is given by the quantitative analysis of the nonlinear signal. Our analytic model is formulated in the framework of the chi(3) nonlinear response, including coulomb interaction between biexcitons and free electron-hole pairs lying in the first Van Hove singularity. A Fano factor of about q = 5 is determined, which drives us to the estimation of biexciton's Auger recombinaison rate B ∈ [0.1; 1] μm · ps−1 . The Biexciton's radiative yield is then estimated of the order of 10−6 .In order to study nanotubes in plasmonic cavities, we developed micro-photoluminescence and dark-field spectroscopy experiments in the optical fiber telecommunication wavelengths (1.3 μm and 1.55 μm). Caracterisation of nanotube samples and plasmonic antenna are presented. Preliminary results on nanotubes inserted in a patch antenna have shown correlation between antenna's position and the spatial distribution of luminescence. Moreover, a change in the carbon nanotube's photoluminescence profile is observed. These results appear to be a turning point in our work. The calibration of our experiment is at its end and studies of optical properties of carbon nanotubes coupled to plasmonic antenna are now on stream in our team.

Far-field optical spectroscopy allows for measurement of plasmonic resonances on metallic nanostructures of various shapes and sizes when illuminated by continuous light. Employing dark-field microscopy makes it possible to measure scattering on a localised plasmon excited on a single, isolated nanostructure. For the purpose of these measurements an apparatus based on commercial dual microscope system Nanonics has been put together. Experiments carried out during work on this thesis have shown a great sensitivity of the apparatus in its present form, allowing to measure a plasmonic resonance of a single nanoparticle. Proposed improvements of the apparatus should lead to even greater sensitivity and precision of measurements in the near future.

This thesis deals with the dark-field imaging and the optical spectroscopy of optically trapped plasmonic nanoparticles. The optical trapping and the characterization of a single particle or multiple nanoparticles as well are demonstrated. The number of the optically trapped particles can be estimated from the dark-field scattering intensity. Experiments show the presence of the interparticle coupling among trapped metallic nanoparticles which has not been observed in case of dielectric particles. The scattering spectra of the plasmonic nanoparticles were compared with theoretical models based on the Mie theory and the Discrete dipole approximation.

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