The dissertation presents theoretical and experimental studies on the physical origin of the signal in photothermal microscopy of single particles. This noninvasive optical far field microscopy scheme allows the imaging and detection of single absorbing nanoparticles. Based on a heat-induced pertur- bation in the refractive index in the embedding medium of the nanoscopic absorber, a corresponding probe beam modification is measured and quantified. The method is well established and has been applied since its first demonstration in 2002 to the imaging and characterization of various absorbing particle species, such as quantum dots, single molecules and nanoparticles of different shapes. The extensive theoretical developments presented in this thesis provide the first quantitative assess- ment of the signal and at the same time enlarge its phenomenology and thereby its potential. On the basis of several approximation schemes to the Maxwell equations, which fundamentally gov- ern the interaction of light with inhomogeneities, several complementing models are devised which describe the photothermal signal both qualitatively and quantitatively. In succession an interdepen- dent and self-consistent set of theoretical descriptions is given and allows important experimental consequences to be drawn. In consequence, the photothermal signal is shown to correspond to the action of a nanoscopic (thermal) lens, represented by the spherically symmetric refractive index pro- file n(r) which accompanies the thermal expansion of the absorber’s environment. The achieved quantification allows the direct measurement of absorption cross-sections of nanoparticles. Further, a qualitatively new phenomenology of the signal is unraveled and experimentally demonstrated. The separate roles of the probing and the heating beams in photothermal microscopy is dismantled and the influence of their relative alignment shown to allow for a controlled adjustment of the effective detection volume. For the first time, both positive and negative signals are demonstrated to occur and to be the characteristic signature of the lens-like action on the probe beam. The detection of the probe beam’s modification is also shown to sensitively depend on the aperture used in the detection chan- nel, and a signal optimization is shown to be feasible. Also, a generalization of the detectable signal via the use of a quadrant photodiode is achieved. Specifically, measuring the far field beam deflec- tion the result of the beam passing the lens off-center manifests in a laterally split detection volume. Hereby, finally each classical photothermal spectroscopic techniques has been shown to possess its microscopic counterpart. Central to the understanding of this generalized and new phenomenology is a scalar wave-optical model which draws an analogy between the scattering of a massive particle wave-packet by a Coulomb potential and the deflection of a focused beam by a photonic potential connected with the thermal lens. The significance of the findings is demonstrated by its methodological implications on photother- mal correlation spectroscopy in which the diffusion dynamics of absorbing colloidal particles can be studied. The unique split focal detection volumes are shown to allow the sensitive measurement of a deterministic velocity field. Finally, the method is supplemented by a newly introduced sta- tistical analysis method which is capable of characterizing samples containing a heterogeneous size distribution.:Contents Bibliographic description Abbreviations 1 Introduction 2 Theoretical Background 2.1 The current literature on the subject of the photothermal signal 2.2 Thermal conduction, and the temperature field around heated nanoparticles 2.3 The linear thermo-refractive response and the thermal lens 2.4 MAXWELL equations and approximation schemes 2.4.1 The MAXWELL equations 2.4.2 HELMHOLTZ equations 2.4.3 Paraxial HELMHOLTZ equation for the field components 2.4.4 Geometrical optics and the eikonal ansatz 2.5 Diffraction and the optical resolution limit in far field microscopy 2.5.1 Transmission scanning microscopy 2.5.2 Point spread functions and aberrations 2.5.3 Scalar diffraction approximation for weakly focused beams 2.5.4 Vectorial diffraction for highly focused electromagnetic fields 2.5.5 Theoretical description of transmission signals 2.6 Elastic scattering of light 2.6.1 Overview of optical elastic scattering theory 2.6.2 The integral equation of potential scattering and the BORN approximation 2.6.3 The generalized LORENZ-MIE theory 2.6.4 The electromagnetic fields 2.6.5 Description of the incident field: beam shape coefficients 2.6.6 Multilayered scatterers 2.6.7 POYNTING vector and field decomposition 2.6.8 Energy balance & total cross-sections 2.6.9 Optical theorem & the extinction paradox 2.6.10 Small particle scattering: the RAYLEIGH-limit 2.7 Optical properties of gold nanoparticles & Surface plasmon resonances 2.7.1 Dielectric function of gold 2.7.2 Total cross-sections of plasmonic nanoparticles properties of gold nanoparticles & Surface plasmon resonances 2.8 (Hot) BROWNian motion, diffusion and their statistical analysis 2.8.1 (Hot) BROWNian motion 2.8.2 Diffusion and correlation analysis 2.8.3 Methods regarding the signal statistics of diffusing tracer particles 2.9 RUTHERFORD scattering of charged particles 2.9.1 Classical RUTHERFORD scattering 2.9.2 Quantum mechanical COULOMB scattering 3 Experimental Setup 3.1 Sample preparation 3.2 Photothermal microscopy setup 4 Photothermal Imaging: Results and Discussion 4.1 MAXWELL equations: Exact treatment of the PT signal 4.1.1 Angularly resolved powers: Fractional cross-sections 4.1.2 Incident power and background normalization 4.1.3 Fractional scattering and extinction cross-sections (off-axis) 4.1.4 Fractional scattering and extinction cross-sections (on-axis) 4.1.5 Small particle approximation(on-axis) 4.1.6 General properties of transmission scans 4.1.7 The thermal lens n(r) in the MIE-scattering framework 4.1.8 The photothermal signal F in the MIE scattering framework 4.2 Geometrical optics: Photonic RUTHERFORD scattering (ray optics) 4.2.1 FERMAT’s principle for a thermal lens medium 4.2.2 Gaussian beam transformation by a thermal lens 4.2.3 Experiments using weakly focused, i.e. nearly Gaussian beams 4.3 HELMHOLTZ equation: Photonic RUTHERFORD scattering (wave optics) 4.3.1 Plane-wave scattering 4.3.2 Focused beam scattering 4.3.3 Connection to the far field 4.3.4 Photothermal Rutherford scattering microscopy 4.3.5 Photothermal half-aperture measurements 4.4 Paraxial HELMHOLTZ equation: FRESNEL diffraction by a thermal lens 4.4.1 The diffraction integral and the phase mask for a thermal lens 4.4.2 The photothermal signal expressed via the image plane field 4.4.3 Experimental demonstration of the signal inversion 4.4.4 Connection to photothermal RUTHERFORD scattering 4.5 Plane-wave extinction & scattering by a thermal lens 4.5.1 The BORN approximation for the ideal and time-dependent thermal lens 4.5.2 The eikonal approximation for the ideal thermal lens and x>>1 4.5.3 Lessons to be learned from plane-wave scattering by thermal lenses 4.6 What is a lens? And is n(r) a lens? 5 Methodological Applications of the Results 5.1 Generalized photothermal correlation spectroscopy (incl. twin-PhoCS) 5.2 Photothermal signal distribution analysis (PhoSDA) 6 Summary and Outlook 6.1 Summary of the results 6.2 Outlook 7 Appendix 7.1 Material parameters 7.2 Calculation parameters 7.3 Interactive simulation scripts (Processing) 7.4 Vectorial scattering in the BORN-approximation 7.5 Details regarding the scattering framework 7.5.1 Connection between Gmn,TE,TM of Ref.1 and gmn,TE,TM in the GLMT 7.5.2 Off-axis BSCs including aberration (single interface) 7.5.3 Details on the incidence power Pinc 7.5.4 Details on the incidence power Pinc for arbitrary beams 7.5.5 Explicit expressions for the spherical field components of Es,i and Hs,i 7.5.6 Note on the time-dependence and the corresponding sign-conventions in M 7.5.7 Recurrence relation for Pn and tn 7.5.8 Gaussian beam shape coefficients: Off-axis 7.5.9 Multilayered Scatterer 7.5.10 POYNTING-vector and energy flow fields 7.5.11 Convergence 7.5.12 Further evaluations in the GLMT framework 7.5.13 Diffraction model: Comparison of angular PT signal pattern to the GLMT 7.6 Details on geometrical optics models 7.6.1 Geometrical optics: Exact solution r(f) for |bx|<1 7.6.2 Correspondences in photonic and partile RUTHERFORD scattering 7.6.3 On the difference in the definition of optical energy 7.6.4 Ray-opticsphotothermalsignal 7.6.5 Thick lens raytracing and the equivalent lens shape for a given aberration 7.7 Thermal lens around a wire of radius R 7.8 Twin-PhoCS: Graphic illustration of the CCF integrand Curriculum Vitae Publications Declaration Acknowledgements List of Tables List of Figures Bibliography

Les nanomatériaux suscitent depuis quelques décennies de plus en plus d’intérêt tant sur le plan des études fondamentales que sur celui des applications. Parmi ces nouveaux matériaux, les nanotubes de carbone ont attiré beaucoup d’attention au sein de la communauté scientifique à cause de leurs propriétés physiques remarquables. Les travaux présentés dans cette thèse, concernent l’élaboration et la caractérisation de composites solides à base de nanotubes de carbone. Le choix des matériaux s’est porté sur une matrice solide à base de Bromure de Potassium (KBr) et des nanotubes de carbone mono et multifeuillets (SWNT, MWNT). L’étude de ces composites concerne deux aspects : dans un premier temps, l’effet de la charge et de la nature des nanotubes de carbone sur les propriétés électriques et thermiques ont été étudiés. L’étude des propriétés thermiques a été réalisée à l’aide d’une technique photothermique, la photoacoustique, qui présente un grand avantage pour ce type de composites. L’évolution des propriétés thermiques en fonction de la charge a montré un comportement atypique, une augmentation puis une diminution, avec un maximum autour de 2% de charge en nanotubes. Un modèle physique permettant de décrire cette évolution a été proposé. Concernant les propriétés électriques, cette étude a permis de mettre en évidence le phénomène de percolation et d’en déterminer le seuil. Dans un deuxième temps, l’étude a porté sur l’influence du gaz environnant sur les propriétés thermiques et électriques, et sur l’éventuelle utilisation de ces composites comme capteurs de gaz. La caractérisation thermique en présence d’éthanol n’a pas permis de mettre en évidence un changement notable des propriétés thermiques des composites. En revanche, la caractérisation électrique a montré une bonne réponse à ce gaz. L’évolution de la sensibilité en fonction de la charge en nanotubes dans les composites a montré une augmentation pour des charges inférieures à 4% et une stabilisation au-delà. L’influence d’autre gaz comme le dioxyde d’azote et le toluène a été aussi étudié. La réponse électrique au dioxyde d’azote a montré une forte interaction du gaz avec les composites. La réponse au toluène n’a pas montré d’influence de ce gaz sur les propriétés électriques des composites à base de SWNT, cependant, dans le cas des composites à base de MWNT, une réponse électrique comparable à celle de l’éthanol a été observée. / In the recent decades, nanomaterials arouse a growing interest both in their fundamental studies and in their applications. Among these new materials, carbon nanotubes have attracted much attention within the scientific community because of their remarkable physical properties.The work presented in this thesis, involve the preparation and characterization of solid composites based on carbon nanotubes. A solid matrix containing potassium bromide (KBr) and carbon nanotubes, single and multiwalled (SWNT, MWNT) was chosen. The study of these composites involves two aspects: initially, the effect of the loading fraction and the nature of carbon nanotubes on the electrical and thermal properties were investigated. The study of thermal properties was carried out by a photothermal technique, the photoacoustic, which offers great advantages for this type of composites. The evolution of thermal properties according to the loading fraction of nanotubes showed an atypical behavior, an increase followed by a decrease, with a maximum around 2% of nanotubes loading fraction. A physical model describing this evolution has been proposed. Regarding the electrical properties, this study has highlighted the phenomenon of percolation and allowed the determination of the percolation threshold. In a second step, the study focused on the influence of surrounding gas on the thermal and electrical properties, and the possible use of these composites as gas sensors. The thermal characterization with ethanol did not reveal a significant change in thermal properties of composites. However, the electrical characterization showed a good response to this gas. The evolution of the sensitivity depending on the nanotubes loading fraction in the composites showed an increase for loads below 4% and a stabilization beyond this value. The influence of other gases such as nitrogen dioxide and toluene were also studied. The electrical response to nitrogen dioxide showed a strong interaction of the gas with composites. The response to toluene did not show any influence of this gas on the electrical properties of SWNT-based composites, however, in the case of MWNT-based composite, an electrical response similar to that of ethanol was observed.

Dans les applications nucléaires, les propriétés des matériaux peuvent subir des modifications importantes en raison de l'interaction destructive avec l'irradiation de particules au niveau des microstructures, qui affectent les propriétés globales. L'un des défis associés aux études de matériaux irradiés par des ions, c'est que la couche concernée, ou la profondeur de pénétration, est généralement très mince (0,1-100 um). Cette étude élargit la base des connaissances actuelles en matière de transport thermique dans les matériaux irradiés par des ions, en utilisant une approche expérimentale multiéchelles avec des méthodes basées sur des ondes thermiques. D'une manière pas encore explorée auparavant, quatre méthodes sont utilisées pour caractériser la couche irradiée par des protons dans ZrC : la microscopie thermique à balayage (SThM), la radiométrie photothermique (PTR) avec détection sur la face avant et balayage spatial, la thermographie infrarouge lock-In (IRT), et la PTR tomographique avec balayage en fréquence. Pour la première fois, le profil de conductivité thermique en profondeur d'un échantillon irradié est mesuré directement. Les profils obtenus par chacune des méthodes d'analyse spatiale sont comparés les uns aux autres et à la prévision numérique du profil endommagé. La nature complémentaire des différentes techniques valide le profil mesuré et la dégradation constatée de la conductivité thermique de l'échantillon de ZrC. / In nuclear applications, material properties can undergo significant alteration due to destructive interaction with irradiating particles at microstructural levels that affect bulk properties. One of the challenges associated with studies of ion-Irradiated materials is that the affected layer, or penetration depth, is typically very thin (~0.1-100 μm). This study expands the current knowledge base regarding thermal transport in ion-Irradiated materials through the use of a multiscaled experimental approach using thermal wave methods. In a manner not previously explored, four thermal wave methods are used to characterize the proton-Irradiated layer in ZrC including scanning thermal microscopy (SThM), spatial-Scanning front-Detection photothermal radiometry (PTR), lock-In IR thermography (lock-In IRT), and tomographic, frequency-Based PTR. For the first time, the in-Depth thermal conductivity profile of an irradiated sample is measured directly. The profiles obtained by each of the spatial scanning methods are compared to each other and the numerical prediction of the ion-Damage profile. The complementary nature of the various techniques validates the measured profile and the measured degradation of thermal conductivity in the ZrC sample.

Neste trabalho estudamos as propriedades térmicas e óticas de íons emissores usando as técnicas de lente térmica e z-scan, resolvidas no tempo. Foram obtidos o espectro fototérmico de lente térmica de amostras dopadas com Yb3+ e diversos outros parâmetros fototérmicos. Foi também realizado um estudo dos efeitos da saturação da não linearidade ótica sobre a determinação das propriedades eletrônicas em sólidos dopados com Cr3+, utilizando a técnica de z-scan. A seguir a mesma técnica foi aplicada na obtenção do parâmetro de upconversion em materiais dopados com Nd3+ e Cr3+ (com excitação ressonante e não ressonante ao nível laser emissor). Empregando a integral de difração foram investigados os efeitos do processo de upconversion Auger sobre a refração não linear. Os resultados experimentais e numéricos mostraram uma excelente concordância. Também foi investigado o comportamento temporal da população do nível emissor na fase de excitação, demonstrando assim uma forma alternativa de obter o parâmetro de upconversion. Finalmente, usando a técnica de z-scan obtivemos a forma de linha da não linearidade ótica de uma amostra dopada com Yb3+ onde demonstramos que a contribuição mais importante para a não linearidade do íon advém de transições no UV, mesmo estando o íon sob excitação ressonante ao nível emissor. / In this work we have studied the thermal and optical properties of emitters ions by using the thermal lens and z-scan time resolved techniques. It was obtained the thermal lens photothermal spectra of Yb3+ doped samples, and several other photothermal parameters. Also, it was done a study on the optical nonlinearity saturation effects over the determination of the optical properties in Cr3+ doped solids, using the z-scan technique. In the sequence the same technique was used in order to obtain the upconversion parameter in Nd3+ and Cr3+ doped materials (with excitation resonant and non resonant to the emitter level). Employing the diffraction integral, the effects of Auger upconversion process on the nonlinear refraction were investigated. The experimental and numerical results agree very well. It was also investigated the temporal behavior of the emitter level population during the excitation process, showing an alternative way to obtain the upconvertion parameter. Finally, by using the z-scan technique we have obtained the optical nonlinear lineshape of a Yb3+ doped sample, and demonstrated that the major contribution to the optical non linearity arises from the UV transitions, even when the emitter level of the ion is under resonant excitation.

Maintaining a constant supply of clean drinking water is among the most pressing global challenges in our time. About one-third of the population is affected by the water scarcity and it can only get worse with climate change, rapid industrialization, and the population growth. Even though nearly 70 percent of the planet is covered by water, the consumable freshwater content is only 2.5 percent of it. Unfortunately, the accessible portion of it is only 1 percent. Even so, most of the freshwater bodies are choked with pollution. Considering the vast availability of saline water on the planet and the increasing wastewater generation, seawater desalination, and wastewater treatment and recycling seem to have the potential to address current water-related issues. Therefore, it is necessary to find efficient techniques for seawater desalination and wastewater treatment. The use of nanostructured materials for these applications is becoming a popular approach due to the unique chemical and physical properties they possess compared to bulk materials Solar energy is the cleanest and most abundant renewable natural resource available. Materials for solar photothermal energy conversion are highly sought after for their cost savings, clean environment, and broad utility in providing water heating and/or steam for many applications including domestic water heating and solar-driven desalination. Extensive research efforts have been made to develop efficient solar absorbers with characteristics such as low weight, low thermal conductivity, broad solar absorption and porosity to be able to float on water to provide more efficient and cost-effective solar steam generation systems. Metal NPs have been proposed to take advantage of the high efficiency of the photothermal energy conversion associated with surface plasmon resonance absorption. Nanostructured carbon-based materials such as graphene oxide, carbon nanotubes, carbonized biomass are also in use due to their excellent photothermal energy conversion ability over the range of the visible and near infra-red region of the electromagnetic spectrum. In this dissertation, five projects based on the utility of nanostructured materials for desalination, photocatalysis and water treatment will be discussed. The first three projects involve the fabrication and design of plasmonic and carbon-based photothermal materials for applications in solar steam generation, water desalination, and wastewater treatment. In the fourth project, a unique shape of ZnO nanostructure was synthesized for photodegradation of organic dyes in industrial wastewater. The final project demonstrates the shape-controlled synthesis of iron carbide nanostructures and composite materials of aminated graphene oxide for the removal of Cr(VI) from wastewater.

Despite the plethora of information regarding cellular crowding and its importance on modulating protein function the effects of confinement on biological molecules are often overlooked when investigating their physiological function. Recently however, the encapsulation of biomolecules in solid state matrices (NafionTM, sol-gels, zirconium phosphate,etc.) has increased in importance as a method for examining protein conformation and dynamics in confined space as well as novel applications in biotechnology. Biotechnological applications include, but are not limited to, bioremediation, biosensors, biocatalysts, etc. In order to better utilize solid state materials as substrates for biological molecules an understanding of the effects of encapsulation on the detailed dynamics associated with physiological function is required as well as a complete characterization of the physical properties associated with the space in which the biological molecule is to be confined. The focus of this research is to probe the effects of confinement on the thermodynamics of ligand photo-release/rebinding to the prototypical heme protein, myoglobin, encapsulated within sol-gel glasses utilizing photoacoustic calorimetry (PAC) and photothermal beam deflection (PBD). Optical spectroscopies (including optical absorption and fluorescence) have also been employed to characterize the molecular environments of materials including Zr-phosphate and metal organic polyhedral (MOPs), thought to be good candidates for novel bio-hybrid materials. The assembly mechanisms associated with MOPs were also examined in order to develop a foundation through which new, bio-compatible MOPs can be designed. Overall the results presented here represent a technological breakthrough in the application of fast calorimetry to the study of proteins in confined space. This will allow for the first time the acquisition of detailed thermodynamic maps associated with the well-choreographed biomolecular dynamics in confined environments.

abstract: Gold nanoparticles as potential diagnostic, therapeutic and sensing systems have a long history of use in medicine, and have expanded to a variety of applications. Gold nanoparticles are attractive in biological applications due to their unique optical, chemical and biological properties. Particularly, gold nanorods (GNRs) are increasingly used due to superior optical property in the near infrared (NIR) window. Light absorbed by the nanorod can be dissipated as heat efficiently or re-emitted by the particle. However, the limitations for clinical translation of gold nanorods include low yields, poor stability, depth-restricted imaging, and resistance of cancer cells to hyperthermia, are severe. A novel high-throughput synthesis method was employed to significantly increase in yields of solid and porous gold nanorods/wires. Stable functional nanoassemblies and nanomaterials were generated by interfacing gold nanorods with a variety of polymeric and polypeptide-based coatings, resulting in unique properties of polymer-gold nanorod assemblies and composites. Here the use of these modified gold nanorods in a variety of applications including optical sensors, cancer therapeutics, and nanobiomaterials were described. / Dissertation/Thesis / Ph.D. Chemical Engineering 2012

Neste trabalho estudamos as propriedades térmicas e óticas de íons emissores usando as técnicas de lente térmica e z-scan, resolvidas no tempo. Foram obtidos o espectro fototérmico de lente térmica de amostras dopadas com Yb3+ e diversos outros parâmetros fototérmicos. Foi também realizado um estudo dos efeitos da saturação da não linearidade ótica sobre a determinação das propriedades eletrônicas em sólidos dopados com Cr3+, utilizando a técnica de z-scan. A seguir a mesma técnica foi aplicada na obtenção do parâmetro de upconversion em materiais dopados com Nd3+ e Cr3+ (com excitação ressonante e não ressonante ao nível laser emissor). Empregando a integral de difração foram investigados os efeitos do processo de upconversion Auger sobre a refração não linear. Os resultados experimentais e numéricos mostraram uma excelente concordância. Também foi investigado o comportamento temporal da população do nível emissor na fase de excitação, demonstrando assim uma forma alternativa de obter o parâmetro de upconversion. Finalmente, usando a técnica de z-scan obtivemos a forma de linha da não linearidade ótica de uma amostra dopada com Yb3+ onde demonstramos que a contribuição mais importante para a não linearidade do íon advém de transições no UV, mesmo estando o íon sob excitação ressonante ao nível emissor. / In this work we have studied the thermal and optical properties of emitters ions by using the thermal lens and z-scan time resolved techniques. It was obtained the thermal lens photothermal spectra of Yb3+ doped samples, and several other photothermal parameters. Also, it was done a study on the optical nonlinearity saturation effects over the determination of the optical properties in Cr3+ doped solids, using the z-scan technique. In the sequence the same technique was used in order to obtain the upconversion parameter in Nd3+ and Cr3+ doped materials (with excitation resonant and non resonant to the emitter level). Employing the diffraction integral, the effects of Auger upconversion process on the nonlinear refraction were investigated. The experimental and numerical results agree very well. It was also investigated the temporal behavior of the emitter level population during the excitation process, showing an alternative way to obtain the upconvertion parameter. Finally, by using the z-scan technique we have obtained the optical nonlinear lineshape of a Yb3+ doped sample, and demonstrated that the major contribution to the optical non linearity arises from the UV transitions, even when the emitter level of the ion is under resonant excitation.

Orientador: Antonio Manoel Mansanares / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Fisica Gleb Wataghin / Made available in DSpace on 2018-08-05T01:51:31Z (GMT). No. of bitstreams: 1 Soffner_MaxErik_M.pdf: 11770260 bytes, checksum: a38f679b7118b0715ab2398a3b6eab6d (MD5) Previous issue date: 2005 / Resumo: Os vidros dopados com semicondutores são objeto de grande interesse pois, em geral, apresentam fortes não-linearidades ópticas e tempos de resposta curtos, devido ao efeito de confinamento quântico que estes materiais apresentam. Neste trabalho, utilizamos a técnica de lente térmica para determinar a difusividade térmica ( a ) e o comportamento da variação do índice de refração com a temperatura ( dn/dT ) em vidros borossilicatos dopados com CdTe com diferentes tempos de tratamento térmico a 540 º C. Os resultados da lente térmica mostraram o aparecimento de um comportamento anômalo para altas intensidades do laser de excitação, que consiste numa queda do sinal para tempos de medida longos. Tal característica foi comprovada com outra técnica fototérmica, a do efeito miragem. Uma possível explicção para esse comportamento é a saturação dos níveis eletrônicos do ponto quântico. A supressão da respectiva banda de absorção reduz o índice de refração para freqüências mais baixas, dando origem a uma lente divergente, compatível com a queda observada no sinal / Abstract: Semiconductor doped glasses are of great interest because of their non-linear optical properties and short response time due to quantum confinement. In this work, we used the thermal lens technique to determine the thermal diffusivity (a ) and the behavior of the temperature coefficient of the refractive index (dn/dT ) in CdTe doped borosilicate glasses treated at 540 º C for different time intervals. The thermal lens measurements showed an anomalous behavior at high intensities of the excitacion beam, which consists in a signal reduction for long acquisition time. This characteristics was confirmed using another photothermal technique, namely, the mirage effect. One possible explanation for this behavior is the saturation of the electronic levels of the quantum-dot. The suppresion of a given absorption band reduces the refractive index at lower frequencies, thus originating a divergent lens, which is in agreement with the observed signal reduction / Mestrado / Física da Matéria Condensada / Mestre em Física

Ces travaux de thèse portent sur la caractérisation thermique à l’échelle micrométrique d’un alliage à base de tellure lorsque ce matériau se trouve à l’état fondu, à haute température. À cette fin, une cellule innovante d’emprisonnement du matériau fondu a été conçue, et mise en place. Des structures de tellure au volume du microlitre ont été déposées sur un substrat de silicium et recouverts par la suite d’une couche de protection capable de les emprisonner dans une matrice : silice amorphe et alumine amorphe. La technique de la Radiométrie Photothermique Modulée a été utilisée pour étudier les propriétés thermiques de ce type de cellules et de ces constituants. La résistance thermique de dépôt a été ainsi estimée en utilisant un modèle d’étude des transferts de la chaleur utilisant le formalisme des impédances thermiques. Ceci nous a permit dans le cas de l’alumine amorphe de déterminer sa conductivité thermique et la résistance thermique de contact avec le substrat jusqu’à 600°C. Un long processus de conception, de mesure et d’analyse a été nécessaire afin d’obtenir une cellule capable de résister aux contraintes des hautes températures. À l’heure actuelle seule la caractérisation thermique jusqu’à 300°C a été possible à cause de l’instabilité mécanique de ce dépôt hétérogène. Ceci a été confirmé par des caractérisations physico-chimiques par techniques XRR, XRD et SEM. / This thesis is devoted to the thermal characterization of molten materials, namely chalcogenide glass-type tellurium alloys, at the micrometer scale. An experimental setup of Photothermal Radiometry (PTR), formerly developed for solid state measurements, has been adapted for this purpose. Using MOCVD technique, a random lattice of sub-micrometric tellurium alloy structures is grown on a thermally oxidized silicon substrate. These structures are then embedded in a protective layer (silica or alumina) to prevent evaporation during melting. Measurements are then performed from room temperature up to 650°C. SEM and XRD measurements performed after annealing show that these samples withstand thermal stress only up to 300°C. The coating’s thermal boundary resistance is estimated by a heat transfer model based on the thermal impedance formalism. Moreover, the thermal conductivity and thermal boundary resistance of thin amorphous alumina by low temperature ALD are measured from the room temperature to 600°C.