Title: Study of light-harvesting antennae based on bacteriolorophyll aggregates Author: Jan Alster Department: Department of Chemical Physics and Optics Supervisor of the doctoral thesis: doc. RNDr. Jakub Pšenčík, Ph.D. Abstract: Artificial photosynthesis is a potential future source of renewable energy. e light-to-emical energy conversion process starts with capturing light. Chlorosomes of green phototropic bacteria are probably the most efficient light-harvesting antenna found in the Nature. Moreover, their unique structure based on a self-organised ag- gregate of pigment molecules makes them relatively easy to mimic in vitro. is work explores formation and properties of self-assembled aggregates of bacteriolorophyll molecules in aqueous solvents by means of steady state and time resolved optical spec- troscopy with time resolution in the microsecond to femtosecond range. Various ag- gregation inducing agents have been tested. Isoprenoid quinones introduce a redox- dependent excitation energy quening meanism into the bacteriolorophyll aggre- gates. Carotenoids enhance the light-harvesting properties of the aggregates by cap- turing light in the spectral region where bacteriolorophyll does not and transferring the excitation energy to bacteriolorophyll. e results indicate that self-assembled...

京都大学 / 0048 / 新制・課程博士 / 博士(エネルギー科学) / 甲第19096号 / エネ博第320号 / 新制||エネ||65(附属図書館) / 32047 / 京都大学大学院エネルギー科学研究科エネルギー応用科学専攻 / (主査)教授 松田 一成, 教授 岸本 泰明, 教授 大垣 英明 / 学位規則第4条第1項該当 / Doctor of Energy Science / Kyoto University / DFAM

The optical spectroscopy techniques have been used to investigate left-handed behavior of metamaterials as well as the electron-bosonic spectral functions (or Bosonic spectra) of high-transition-temperature superconductors (or high-Tc superconductors) in the research work of this thesis. The periodic double-ring split-ring resonator (SRR) array was one of the first proposed magnetic metamaterials which could give rise to a negative magnetic permeability (μ<0). In the traditional design of negative index metamaterials, the SRR arrays were combined with continuous metallic wires that provide a negative electric permittivity (∊<0). However, the requirement of an unbroken electrical connection between unit cells would be challenging in building contoured devices. In our study, we carefully examine the electromagnetic properties of the double-ring SRR arrays on silicon substrates in the mid-infrared frequency regime experimentally and numerically. For light at normal incidence, we observe that an electric resonance in the outer ring and a magnetic resonance in the inner ring exist at similar frequencies in one of our samples, which suggests that the double-ring SRR array could have simultaneous a negative permittivity and a negative permeability, or a left-handed behavior. Our conjectures are confirmed by the numerical simulations. We also propose a new left-handed metamaterial composed of two single-ring SRRs in each unit cell. The left-handed behaviors in our designs originate from the SRR structure itself only and therefore, there are no metallic continuous wires involved compared to the conventional left-handed SRR metamaterials. The high-Tc superconductor samples studied here are highly under-doped YBa2Cu3O6.35 (YBCO6.35), nearly optimally doped monolayer HgBa2CuO4+ઠ (Hg1201), Zn- and Ni- doped Bi2Sr2CaCu2O8+ઠ (Bi2212) single crystals. We experimentally determine the optical constants of the samples and numerically extract the electronboson spectral functions from the optical scattering rate by either an analytic formula or a maximum entropy inversion technique. We find that the bosonic mode obtained from the optical data is consistent with a peak in the q-averaged susceptibility seen in the magnetic neutron scattering studies. The comparisons of the bosonic spectra between YBCO6.35 and YBCO6.50, monolayer Hg1201 and trilayer Hg1223 (HgBa2Ca2Cu3O8+ઠ), Zn-doped and Ni-doped Bi2212 characterize the variation of the bosonic spectra with the hole concentration, Tc as well as the magnetic and nonmagnetic atom substitution. / Thesis / Doctor of Philosophy (PhD)

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Diese Dissertation konzentriert sich auf die Untersuchung der Schwingungs- und exzitonischen Eigenschaften von zweidimensionalen Übergangsmetall-Dichalkogeniden (TMDCs) unter Verwendung von mikro- und nanooptischer Spektroskopie. Im ersten Teil der Arbeit wird Mikro-Raman-Spektroskopie verwendet, um die Schwingungseigenschaften von 2D-TMDC-Homo- und Heterostrukturen zu untersuchen, mit dem Ziel, die Hochfrequenz-Raman-Signatur für die Wechselwirkung zwischen den Schichten und die Gitterdynamik zu erforschen. Basierend auf einer systematischen Raman-Studie, unterstützt durch Photolumineszenz- (PL) und Topographie-Untersuchungen an nicht gekoppelten und gekoppelten TMDC-Doppellagen, wird die aus der Ebene herausragende $B_{2g}$-Schwingungsmode experimentell als ein charakteristischer Raman-Fingerabdruck zur Einschätzung der Wechselwirkung zwischen den Schichten in 2D-TMDC-Systemen erklärt. Darüber hinaus wird anhand eines Beispiels mit verdrehter Doppellage (tB) von WSe$_2$ als typisches TMDC gezeigt, dass das Raman-Intensitätsverhältnis der beiden Peaks $I_{B_{2g}}/I_{{E_{2g}}/{A_{1g}}}$ mit der Entwicklung der Moiré-Periode korreliert. Mit einer Reihe temperaturabhängiger Raman- und Photolumineszenz-Messungen sowie \textit{ab initio}-Berechnungen wird das Intensitätsverhältnis $I_{B_{2g}}/I_{{E_{2g}}/{A_{1g}}}$ als Signatur der Gitterdynamik in tB-WSe$_2$-Moiré-Übergittern erklärt. Durch die weitere Untersuchung verschiedener Materialkombinationen von verdrehten Hetero-Doppellagen werden die Ergebnisse auf alle Arten von Mo- und W-basierten TMDCs erweitert. Im zweiten Teil der Dissertation wird die spitzenverstärkte Photolumineszenz-Spektroskopie (TEPL) eingesetzt, um die konventionelle optische Auflösungsgrenze zu überwinden und die konkurrierenden Mechanismen der lokalen Photolumineszenz-Dämpfung und -Verstärkung an 2D-TMDC/hBN/Plasmonik-Grenzflächen zu verstehen. Durch den Vergleich verschiedener Nahfeldemissions-Eigenschaften und TEPL-Spektren in Abhängigkeit von der Spitzen-Proben-Entfernung an einer komplexen Monolagen-MoSe$_2$/hBN/NT/SiO$_2$-Probe werden die lokalisierte Oberflächenplasmonenresonanz (LSPR), die Elektronen-Dotierung und der Tunneltransport sowie hochlokalisierte Belastung als dominierende Faktoren für die lokale PL-Dämpfung und -Verstärkung identifiziert.

In this thesis, the effect of the sample properties on the characteristics of the hot carrier luminescence in graphene is investigated. The present work focuses on the two main issues described below. The first issue is the modification effects of near-infrared pulsed laser excitation on graphene. For excitation fluences several orders of magnitude lower than the optical damage threshold, the interaction with ultrafast laser pulses is found to cause a stable change in the properties of graphene. This photomodification also results in a decrease of the hot photoluminescence intensity. The detailed analysis shows that ultrafast photoexcitation leads to an increase in the local level of hole doping, as well as a change in the mechanical strain. The variation of doping and strain are linked with the enhanced adsorption of atmospheric oxygen caused by the distortion of the graphene surface. These findings demonstrate that ultrashort pulsed excitation can be invasive even if a relatively low laser power is used. Secondly, the variation of the hot photoluminescence intensity with the increasing charge carrier density in graphene is investigated. The electro-optical measurements performed using graphene field-effect transistors show a strong dependence of the photoluminescence intensity on the intrinsic carrier concentration. The emission intensity has a maximum value in undoped graphene and decreases with the increasing doping level. The theoretical calculations performed using a refined two-temperature model suggest that the reduction of the photoluminescence intensity is caused by an increase in the hot carrier relaxation rate. The modification of the carrier relaxation dynamics caused by photoinduced doping is probed directly using the two-pulse correlation measurements. The discovered sensitivity of the hot photoluminescence to the intrinsic carrier concentration can be utilised for spatially-resolved measurements of the Fermi level position in graphene samples, offering an advantage in resolution and speed.

Optical spectroscopy combined with mass spectrometry provides a unique opportunity to probe the intrinsic properties of biologically-relevant ions in the gas phase, free from the interfering effects of solvent interactions in the condensed phase. Electrospray ionization allows large biomolecules to be transferred intact into the gas phase for mass analysis. Modern mass spectrometers provide excellent sensitivity, mass-resolution and can efficiently isolate a single ionic species from a complex mixture. However, the extent to which biomolecules retain their solution-phase conformations in the gas phase is largely unknown. Therefore, there is considerable interest in applying spectroscopic methods to biological ions in vacuuo. Due to the low number densities of ions in storage devices, traditional absorption measurements are not feasible, requiring more sensitive analytical methods. Two such techniques are laser-inducedfluorescence (LIF) and photo-dissociation (PD) action spectroscopy, both of which measure the consequence of absorption. The work in this dissertation describes applications of optical spectroscopic methods to interrogate mass-selected ions using a variety of ion storage apparatus including a Fourier transform ion cyclotron resonance mass spectrometer, a quadrupole ion trap and an electrostatic ion storage ring. First, the conformations of small cationized arginine complexes have been investigated using infrared multiple-photon dissociation (IRMPD) action spectroscopy in the IR fingerprint region of the spectrum (200-1800 cm-1). Second, an apparatus incorporating a quadrupole ion trap has been constructed in our laboratory to perform LIF and PD-action spectroscopy. The gas-phase fluorescence and photodissociation properties of three Rhodamine dyes have been investigated including fluorescence excitation and dispersed fluorescence spectra. Finally, the latter chapters describe the use of electronic action spectroscopy to investigate a model chromophore of the green fluorescent protein (GFP), p-hydroxybenzylidene-2,3-dimethylimidazolone (HBDI). The body of work in this dissertation highlights the integration of gas-phase spectroscopy and mass spectrometry to elucidate the fundamental photophysical properties of biological and related ions.

La menace d’attaques terroristes reste omniprésente dans de nombreux lieux à forte fréquentation. Une technique capable de détecter les substances explosives est donc nécessaire pour traiter au mieux cette menace. Initié par le Ministère de la Défense et la Direction générale de l’Armement, le projet REI ExploLIBS a pour but d’étudier le potentiel de la spectroscopie de plasma induit par laser à détecter les résidus d’explosifs. Des études expérimentales et théoriques sont menées par Bertin Technologies en collaboration avec le laboratoire LP3 – UMR 6182. L’ablation de polymères sous différentes atmosphères a permis de caractériser l’évolution spatio-temporelle de l’émission des molécules CN et C2. Le rayon d’émission, la température et la décroissance de l’intensité sont reliés au processus de formation des molécules. L’analyse complémentaire par le calcul de la composition du plasma en équilibre thermodynamique local permet de mettre en évidence la présence de molécules en fortes concentrations dans le plasma difficiles à visualiser en spectroscopie optique. Ces études ont abouti au développement d’une sonde portable dédiée à la détection des explosifs. Le taux de détection est évalué à plus de 90% et le taux de faux positif inférieur à 5%. La limite actuelle de sensibilité est estimée à 55 µg.cm-2. / The threat of terrorist attacks remains omnipresent in many high traffic sites. A technique capable of detecting explosives is needed to best address this threat. Initiated by the Ministère de la Défense and the Direction Générale de l’Armement, the project REI ExploLIBS aims to explore the potential of laser-induced breakdown spectroscopy to detect explosive residue. Experimental and theoretical studies are carried out by Bertin Technologies in collaboration with the LP3 laboratory – UMR 6182. The ablation of polymers under different atmospheres permits to characterize the spatial and temporal evolution of the emission of the CN and the C2 molecules. The radius of emission, the temperature and the decrease of the intensity are related to the formation process of the molecules. The additional analysis by the calculation of the composition of the plasma in local thermodynamic equilibrium reveals the presence of molecules in high concentrations in the plasma that are difficult to visualise in optical spectroscopy. These studies led to the development of a portable sensor dedicated to the detection of explosives. The detection rate is estimated at over 90% and the false positive rate below 5%. The current sensitivity limit is estimated at 55 µg.cm-2.

De nombreuses applications industrielles nécessitent le dépôt de films métalliques à la surface de polymères afin de conférer une fonction de conduction électrique à ces matériaux isolants. Cette étude a été motivée par la volonté de la société Radiall, dont une partie de l’activité concerne la réalisation de connecteurs à haute performance, de remplacer le procédé de métallisation par voie humide par un procédé de dépôt par voie sèche plasma. Le travail présenté ici porte ainsi sur l’étude du procédé de pulvérisation cathodique magnétron avec ionisation de la vapeur par plasma radiofréquence (RF-IPVD) pour le dépôt de couches minces de cuivre sur substrats de formes complexes en poly-sulfure de phénylène. Cette thèse regroupe d’une part les résultats concernant la métallisation des connecteurs et d’autre part l’analyse de la phase plasma. La validation du procédé RF-IPVD a comporté plusieurs étapes : i) le développement du traitement du polymère par plasma ICP avant dépôt du film de cuivre afin que l’adhérence satisfasse la norme ISO 2409. ii) la détermination des paramètres d’élaboration permettant d’optimiser la conductivité des films et leur conformité sur les substrats 3D. Ces travaux se sont concrétisés par la définition d’un réacteur pilote dans l’optique de réaliser la transposition à l’échelle industrielle du procédé RF-IPVD. Plusieurs études à caractère fondamental ont également été menées afin, d’une part, de comprendre les mécanismes régissant l’adhérence (analyses XPS) et ceux régissant la résistivité (analyses DRX). D’autre part, l’utilisation de divers diagnostics de la phase plasma ont été employés afin de comprendre les mécanismes de transfert d’énergie prenant place dans le milieu gazeux et responsables des propriétés des dépôts. / Many industrial applications require the deposition of metal thin films on polymer surfaces in order to confer electrical conductive function to these insulating materials. This study was motivated by the will of Radiall company, which is a high performance connectors maker, to substitute the chemical bath metallization process by a plasma deposition process. The present work focuses on the study of a magnetron sputtering process with ionization of the mettalic vapor plasma (RF-IPVD) for depositing thin copper films on complex shapes poly-phenylene sulfide substrates. This thesis shows the results for the connectors metallization and also the analysis of the plasma. RF-IPVD process validation involves several steps: i) the development of polymer treatment by ICP plasma before depositing copper films in order to meet ISO 2409 adhesion standard. ii) determining the processing parameters to optimize the conductivity of the films and their compliance on the 3D substrates. The industrial part has been concluded by the definition of a prototype reactor with a view to achieve the implementation of the RF-IPVD process on an industrial scale. Several fundamental studies have been performed to understand the mechanisms governing the adhesion (XPS analysis) and those governing the resistivity (XRD analysis). Moreover, the use of various plasma diagnostics were used to understand the energy transfer mechanisms taking place in the gaseous medium and responsible of the films properties.

Estudamos as propriedades de absorção e emissão de aglomerados Yb2+/CN- em haletos de potássio (KCl, KBr e KI) e estamos propondo um modelo para a estrutura geométrica do aglomerado. Neste modelo o itérbio divalente e o íon cianeto substituem um cátion e um ânion vizinhos, respectivamente, com o eixo que une os dois íons na direção . O acoplamento entre os dois impede o movimento rotacional do cianeto, mesmo à temperatura ambiente, como pode ser comprovado pela presença de linhas estreitas no espectro de absorção infravermelha. Os espectros de absorção visível e ultravioleta são compatíveis com as transições 4&#40214&#8594 4&#40213 5d do itérbio em simetria C4v. A absorção vibracional indica a presença não intencional de OCN- que pode formar aglomerados com os íons cianeto. À temperatura do nitrogênio líquido, observa-se a influência do itérbio sobre os estados rotacionais do cianeto, uma indicação da interação entre centros vizinhos. A excitação sobre as bandas de absorção ultravioleta e visível produz intensa emissão em que podem ser identificadas três regiões (450&#8594;500 nm, 500&#8594;600 nm e acima de 600 nm) com comportamentos distintos quanto à variação da temperatura e excitação. Os tempos de vida variam de 50&#181s à temperatura ambiente até 20 ms à temperatura do hélio líquido. Simultaneamente à emissão visível, observa-se a emissão vibracional-rotacional dos íons cianeto, com indicações de transferência de energia entre os íons cianeto acoplados ao itérbio e os isolados / We have studied the absorption and emission properties of the Yb2+/CN- in potassium halides (KCl, KBr and KI) and it was proposed a structural model for this system. In this model the divalent ytterbium and the cyanide ion substitute a neighboured cation and an anion along a direction. The rotational motion of the cyanide ion is constrained by the coupling with the ytterbium, which is by the presence of narrow lines in the infrared absorption spectra, even at room temperature. The UV and visible absorption spectra are compatibles with the 4&#40214&#8594 4&#40213 5d ytterbium transitions under C4v symmetry. The vibrational absorption reveals the unintentional presence of OCN- that can form clusters with cyanide ions. The influence of the ytterbium over the rotational states of cyanide can be observed at liquid nitrogen temperature, revealing the interaction between both impurities. The optical excitation if the absorption bands shows a broad and strong emission in three regions (450&#8594;500 nm, 500&#8594;600 nm and above 600 nm) with different behaviors under temperature and excitation pump changes. Lifetimes between &#181s at room temperature and 20 ms at liquid heliurn temperature can be observed. Simultaneously to the visible emission, it was observed the vibrational-rotational emission of CN- ions with evidences of energy transfer between coupled Yb<sup<2+/CN- pairs and isolated CN- ions