Orientador: Antonio Manoel Mansanares / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Fisica Gleb Wataghin / Made available in DSpace on 2018-09-26T13:55:51Z (GMT). No. of bitstreams: 1 Freitas_LauraRamosde_D.pdf: 4490607 bytes, checksum: c7b66729395ef47ae8f2ab3bb212544e (MD5) Previous issue date: 2005 / Resumo: A Microscopia Fototérmica de Reflexão vem sendo utilizada na investigação de dispositivos micro e opto-eletrônicos em operação, devido ao seu caráter não destrutivo e por não requerer contato com a superfície da amostra. Esta técnica se baseia na dependência da refletância da amostra com a temperatura, com o campo elétrico local, bem como com a densidade de portadores livres, que são, por sua vez, afetados por defeitos. Este fato torna esta técnica muito adequada para investigar defeitos em processos de fabricação e envelhecimento destas estruturas. Neste trabalho, apresentamos um estudo experimental e teórico sobre a resposta fototérmica em função do comprimento de onda do feixe de prova, para estruturas micro-eletrônicas estratificadas. As amostras consistiram basicamente de trilhas condutoras de silício policristalino de diversos chips. As medidas de termo-refletância foram realizadas na faixa de comprimento de onda de 450nm até 750nm, sendo que as trilhas foram alimentadas sempre com corrente modulada, com três montagens experimentais diferentes. Um padrão oscilatório é observado na região espectral em que a camada superior é transparente. Essas oscilações são causadas pelas múltiplas reflexões nas interfaces. Utilizando um modelo termo-óptico, mostramos que as constantes (n e k), que dependem do comprimento de onda, assim como suas derivadas com relação à temperatura (dn/dT e dk/dT), influenciam fortemente o sinal de termo-refletância. A espessura óptica das camadas, principalmente determinadas pela parte real dos índices de refração, define o período de oscilação. Por outro lado, a parte imaginária estabelece o comprimento de onda em que as oscilações começam. Abaixo de um certo comprimento de onda, a luz de prova não penetra no material e a refletância da camada superficial domina o sinal / Abstract: Photothermal microscopy has been used as a suitable technique for the investigation of micro- and opto-electronic devices in operating cycle, because of its non-contact and non-destructive character. This technique is based on the dependence of the sample reflectance with temperature and with local electric field, as well as with free carrier density, which are in their turn disturbed by defects. This fact makes this technique very useful for investigating defects in fabrication and aging processes of such structures. In the present work, we report an experimental and theoretical study of the thermoreflectance response as a function of the probe wavelength for layered microelectronics structures. The investigated samples consisted of polycrystalline silicon conducting tracks from various chips. Thermore²ectance measurements were carried out in the wavelength range from 450 to 750 nm with the tracks biased in modulated regime, with three diÿerent experimental setups. An oscillating pattern is observed in the spectral region where the upper layer is transparent. Such oscillations are due to the interference resulting from the multiple reflections at the interfaces. Using a thermo-optical model, we show that the optical constants (n and k) of the materials, which are wavelength dependents, as well as their temperature derivatives (dn/dT and dk/dT), strongly in²uence the thermoreflectance signal. The optical thicknesses of the layers, mainly determined by the real part of the refractive indexes, de½ne the period of oscillation. On the other hand, the imaginary part of the refractive indexes establishes the cutoÿ wavelength of the oscillations. Below this cutoÿ wavelength, the probe light does not penetrate the material, and the upper surface reflectance dominates the signal / Doutorado / Física da Matéria Condensada / Doutor em Ciências

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.

Diese Dissertation demonstriert die Nutzung von einzelnen optisch geheizten Goldnanopartikeln als Sensoren f ¨ur die Untersuchung von W¨armetransport und als Intensit¨atsmodulator f ¨ur Licht. Die beschriebenen Experimente basieren auf der photothermischen Mikroskopie, die die selektive Abbildung and Untersuchung von einzelnen absorbierenden Objekten erm¨oglicht. Goldnanopartikel werden optisch angeregt. Die Relaxation erfolgt durch nichtstrahlende Prozesse, die zu einer lokalen Erh¨ohung der Temperatur f ¨uhren. Die Erw¨armung f ¨uhrt zu einer Verringerung der Brechzahl, die als thermische Linse wirkt und dadurch die Ausbreitung eines zweiten nicht absorbierten Lichtstrahls vera¨ndert. Da die thermische A¨ nderung der Brechzahl sehr gering ist, wird das photothermische Signal durch das moduliertes Detektionsverfahren verst¨arkt. Der Heizlaserstrahl wird intensit¨atsmoduliert und erzeugt dadurch eine geringe Modulation der Strahlbreite des Detektionslaserstahls. Damit ver¨andert sich die Leistung, die durch eine Blende transmittiert wird. Diese Modulationsamplitude and Phaseverz¨ogerung werden mittels eines phasenempfindlichen Gleichrichters detektiert. Amplitude und Phase h¨angen von Modulationsfrequenz und thermischer Diffusivit¨at ab. Die frequenzaufgel¨oste Messung der beiden Gr¨oßen und deren Modellierung mittels einer verallgemeinerten Lorenz–Mie Theorie erm¨oglicht die Messung von der thermischen Diffusivit¨at des Mediums, das das Goldnanopartikel umgibt. In der zweiten Variante wird die Ausbreitung der W¨arme beobachtet. Ein Nanopartikel wird optisch geheizt und die ausgedehnte thermische Linse wird mit Hilfe der Ablenkung eines zweiten Laserstrahls vermessen. Das Ablenkungssignal wird mittels eines strahlenoptischen Models berechnet, um die thermische Diffusivit ¨at des Materials zu bestimmen, das das Nanopartikel umgibt. In einem weiteren Experiment wird das große Potential von optisch geheizten Nanopartikeln verdeutlicht. Einzelne Goldnanopartikel werden in eine d¨unne nematische Fl¨ussigkristallschicht eingebettet, deren Dicke darauf abgestimmt ist, dass die Schicht eine l/2-Platte darstellt. Die Goldnanopartikel werden optisch geheizt und steuern damit den Phasen¨ubergang von der nematischen zur isotropen Phase. Damit wird die Transmission eines zweiten Laserstrahls im Polarisationskontrast ge¨andert. Mit Hilfe dieser Anordnung kann die Intensit¨at eines Lichtstrahls um bis zu 100% moduliert werden. / This dissertation demonstrates the use of individual optically heated gold nanoparticles as sensors for investigations of heat transport and intensity modulation of light. The experiments employ the photothermal effect, which allows the selective detection and investigation of individual absorbers. The photothermal contrast is based on absorbing particles that are optically excited and relax via nonradiative processes. The absorbers act as nanosources of heat. The local temperature elevation leads to a local refractive index change due to thermal expansion which then acts as a lens. This thermal lens alters the propagation of a second non-absorbed beam of light. As the refractive index change with temperature is minuscule, the transmission changes of the detection are tiny as well. The photothermal signal is amplified by the use of a modulated detection scheme which enables the methods high sensitivity and provides a time scale for the measurement of thermal transport. The heating laser beam is intensity-modulated and thereby produces a small modulation of the beam waist of the detection laser beam and thus the transmitted power through an aperture. This modulation amplitude and phase are detected by a lock-in amplifier. Amplitude and phase depend on the modulation frequency and the thermal diffusivity of the material surrounding the nanoparticle. The frequency-resolved measurement of the two observables and their modeling using a generalized Lorenz–Mie theory allows the measurement of thermal diffusivities. In the second variant, the spread of heat into space is observed. A nanoparticle is optically heated, and the extended thermal lens is characterized by the deflection of a second laser beam. The deflection signal is modeled using ray optics to determine the thermal diffusivity of the material surrounding the nanoparticle. In a further experiment, the great potential of optically heated nanoparticles is demonstrated. Individual gold nanoparticles are embedded in a thin nematic liquid-crystal layer acting as a half-wave plate. The gold particles are optically heated. They control the transmission of a detection laser set up in polarization contrast. The intensity of the detection beam is modulated by up to 100%.

<div>Vibrational spectroscopic imaging has become an emerging platform for chemical visualization of biomolecules and materials in complex systems. For over a century, both Raman and infrared spectroscopy have demonstrated the capability to recognize molecules of interest by harnessing the characteristic features from molecular fingerprints. With the recent development of hyperspectral vibrational spectroscopy imaging, which records the chemical information without sacrificing the spatial-temporal resolution, numerous discoveries has been achieved in the field of molecular and cellular biology. Despite the ability to provide complimentary chemical information to Raman-based approaches, infrared spectroscopy has not been extensively applied in routine studies due to several fundamental limitations: 1). the poor spatial resolution; 2). inevitable strong water absorption; 3). lack of depth resolution.</div><div>Mid-infrared photothermal (MIP) microscopy overcame all the above mentioned problems and for the first time, enabled depth-resolved in vivo infrared imaging of live cells, microorganisms with submicrometer spatial resolution. The development of epi-detected MIP microscopy further extends its application in pharmaceutical and materials sciences. With the deployment of difference frequency generation and other nonlinear optical techniques, the spectral coverage of the MIP microscopy was significantly enhanced to enable chemical differentiation in complex systems across the broad mid-infrared region. In addition to the efforts to directly improve the performance of MIP microscopy, a novel quantitative phase imaging approach based on polarization wavefront shaping via custom-designed micro-retarder arrays was developed to take advantage of the highly sensitive phase measurement in combination with the photothermal effect. Besides, the extended depth-of-field and multifocus imaging enabled by polarization wavefront shaping could both improve the performance of MIP microscopy for volumetric imaging.</div>

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

<p dir="ltr">The beautiful complexity of our world is manifested in how macro- and even planetary-scale processes are essentially completely determined and regulated by chemical and physical transformations happening at the micro- and nanoscale. The introduction and subsequent development of optical microscopy methods have provided us with a unique opportunity to visualize, probe, and sometimes even control these processes that are too small to be seen by the human eye by their nature.</p><p dir="ltr">Among the great variety of truly impressive advances in microscopy instrumentation, two techniques stand out in their widespread and usefulness. First of them, fluorescence imaging has completely revolutionized the study of biological specimens and living systems due to its unprecedented single-molecule sensitivity and resolution combined with video-rate imaging capability. On the other hand, chemical imaging in the mid-infrared region provides an unmatched amount of chemical information enabling label-free mapping of the spatial distribution of various classes of biological molecules. However, each of these techniques falls short where the other excels. For example, despite its high resolution and sensitivity, fluorescence imaging does not carry direct chemical information and relies on labeling specificity, while infrared microscopy is diffraction-limited at the resolution of several micrometers and suffers from low penetration depth in aqueous solutions.</p><p dir="ltr">This dissertation introduces a novel imaging method designed to combine the advantages of fluorescence imaging and infrared spectroscopy. Fluorescence-detected photothermal mid-IR (F-PTIR) microscopy is presented in <b>chapter 1</b> as a technique enabling sub-diffraction chemically-specific microscopy by detecting local temperature-induced fluctuations in fluorescence intensity to inform on localized mid-infrared absorption. F-PTIR applications in targeted biological microspectroscopy (<b>chapter 1</b>) and pharmaceutical materials (<b>chapters 2 and 3</b>) analysis are demonstrated to highlight the potential of this new method. Furthermore, instrumentation developments relying on modern radiation sources such as dual-comb quantum cascade laser and synchrotron infrared radiation are shown to improve spectral acquisition speed (<b>chapter 4</b>) and spectral coverage (<b>chapter 5</b>), respectively, to extend the application range of F-PTIR.</p>