<p> The optical properties of high temperature superconductors have long been of interest to condensed matter physicists. The majority of the research has concentrated on the steady-state properties of cuprates. Optical excitation of cuprate superconductors provides the valuable opportunity to study the dynamics of the superconducting state via the evolution of the superconducting condensate and excited quasiparticles. Terahertz (THz) spectroscopy is particularly attractive for the study of thin film cuprates, as the energies available in broad spectrum THz pulses lie below the maximum superconducting gap values. Optical pump THz probe spectroscopy utilizes a high energy infrared pulse to destroy the condensate and excite quasiparticles states out of equilibrium. The THz probe is capable of spectrally resolving the sample's temporal response to the optical perturbation. The direct measurement of both the amplitude and phase of the electric fields associated with the transmitted THz radiation allow for the calculation of both the real and imaginary parts of the conductivity. This offers the tantalizing potential of untangling the condensate's recovery from quasi-particle dynamics.</p> <p> The focus of this thesis will be upon the long timescale dynamics of YBa2Cu3O7-δ (YBCO) thin films. It has generally been believed that the condensate is fully recovered after a few picoseconds, and that the recovery of these films at longer timescales is essentially a thermal process although perhaps slowed by a phonon bottleneck. However, we will show spectral evidence that this picture cannot fully explain long lived dynamics in YBCO thin films. Specifically we see a suppression of the low frequency components of the optical conductivity. This anomaly is consistent with the formation of spatial inhomogeneity in the superconducting fraction, which likely arises from a non-uniform formation of the condensate across the film. The role of local inhomogeneity in the condensate and its effect on the conductivity of the thin film will be discussed. Evidence of intrinsic inhomogeneities in YBCO films may prove useful to the theoretical understanding of condensate dynamics in the cuprates. The spectral response of three doping levels, from optimally doped to underdoped YBCO, will also be shown, with a brief discussion of the normal state dynamics in underdoped films and the possible sensitivity of THz radiation to pseudogap dynamics.</p> / Thesis / Doctor of Philosophy (PhD)

Στην παρούσα Ειδική Ερευνητική Εργασία μελετόνται οι φωτοφυσικές ιδιότητες γνωστών χρωμοφόρων μορίων. Συγκεκριμένα μελετάται η Coumarin 30, η Fluorescein Isothiocyanate και η Dichlorofluorescein, τόσο με φασματοσκοπία σταθερής κατάστασης όσο και με φασματοσκοπία χρονικής ανάλυσης μέσω της τεχνικής Time Correlated Single Photon Counting. Η διερεύνηση γίνεται με τα μόρια αυτά να βρίσκονται σε μορφή διαλυμάτων με στόχο τον προσδιορισμό της συμπεριφοράς τους όταν αυτά βρισκονται σε διαφορετικά περιβάλλοντα (διαλύτες). Επιπλέον ερευνώνται οι αλληλεπιδράσεις των μορίων αυτών μέσω της φασματοσκοπίας σταθερής κατάστασης και χρονικής ανάλυσης όταν βρίσκονται σε μορφή μειγμάτων. / In this Master Thesis, the phophysical properties of chromophrores are investigated. Specifically, Coumarin 30, Fluorescein Isothiocyanate and Dichlorofluorescein are studied with steady – state spectroscopy as well as with time – resolved spectroscopy via the technique of Time Correlated Single Photon Counting. The study of these molecules focuses also on solvent – solute effects. Finally, interactions between them are also studied through steady – state spectroscopy and time resolved spectroscopy.

<p>Early processes following photon absorption by the photosynthetic pigment-protein complex photosystem I (PS I) have been the subject of decades of research, yet many questions remain in this area of study. Among the trickiest to investigate is the role of the PS I reaction center’s (RC’s) two accessory (A_‑1) chlorophyll (Chl) cofactors as primary electron donors or acceptors, oxidizing the special pair (P₇₀₀) of Chls or reducing a nominal primary electron acceptor (A₀) Chl in the first electron transfer step. Such processes, which occur on a picosecond timescale, have long been studied via ultrafast spectroscopy, though difficulty lies in distinguishing among signals from early processes, which have similar lifetimes and involve many identical pigments. In this work, we used steady-state and ultrafast optical pump-probe spectroscopies on PS I trimers from wildtype and mutant strains of the cyanobacterium <i>Synechocystis</i> sp. PCC 6803 in which an asparagine amino acid residue near A_‑1 had been replaced with methionine on one or both sides of the RC. We also conducted an identical set of experiments on mutants in which A₀ was similarly targeted, as well as studied the effects on the A₀ absorption spectrum of a third category of mutations in which a peripheral H‑bond to A₀ was lost. Steady-state absorption spectroscopy revealed that many of these mutations caused mild Chl deficiencies in the light-capturing antenna of PS I without necessarily preventing organisms’ growth. More importantly, we determined that contrary to certain hypotheses, A_‑1 is the most likely true first electron acceptor, as reasoned from observing rapid triplet state formation in double A_‑1 mutants. We also concluded from non-additive detrimental effects of single-side mutations that if one RC branch is damaged at the level of A₀ or A_‑1, electron transfer may be redirected along the intact branch. This may help explain the conservation of two functional RC branches in PS I over many generations of natural selection, despite the additional cost to organisms of manufacturing both.</p>

Στην παρούσα Ειδική Ερευνητική Εργασία ερευνώνται οι οπτικές ιδιότητες των νανοκρυσταλλικών κβαντικών τελειών CuInS2/ZnS, γνωστές ως CIS/ZnS QDs, τόσο με τη χρήση φασματοσκοπίας σταθερής κατάστασης όσο και με τη χρήση φασματοσκοπίας χρονικής ανάλυσης με την τεχνική Time Correlated Single Photon Counting. Ειδικότερα, διερευνώνται οι μηχανισμοί που εμπλέκονται στη διαδικασία της εκπομπής φωτός, η επίδραση που έχει η πολικότητα του διαλύτη και η συγκέντρωση των κβαντικών τελειών, όταν είναι διαλυμένες εντός διαλύματος, καθώς και η αλληλεπίδραση μεταξύ των κβαντικών τελειών όταν είναι εναποτιθέμενες σε υμένια, είτε με την τεχνική drop-casting είτε με spin-coating. Τόσο η αύξηση της συγκέντρωσης των κβαντικών τελειών όσο και η αύξηση της πολικότητας του διαλύτη προκάλεσε τη μετατόπιση του εξιτονικού ώμου και του μήκους κύματος μέγιστης εκπομπής προς το ερυθρό, στα φάσματα σταθερής κατάστασης. Επίσης η μετατόπιση της φωτοφωταύγειας των CIS/ZnS QDs προς το ερυθρό ήταν μεγαλύτερη στα υμένια που είχαν παρασκευασθεί με την τεχνική drop-casting από τα υμένια με το ίδιο υπόστρωμα που είχαν παρασκευασθεί με την τεχνική spin-coating. Με χρήση φασματοσκοπίας χρονικής ανάλυσης, ανιχνεύθηκε η ύπαρξη τριών μηχανισμών στα διαλύματα με χρόνους ζωής 1-3, 20-40 και 200-300 ns, ενώ στα υμένια προστέθηκε ένας επιπλέον μηχανισμός με χρόνο ζωής από μερικές εκατοντάδες ps έως 4 ns. Ο χαρακτήρας της αποδιέγερσης των QDs στα υμένια κυμαίνεται μεταξύ διεκθετικού και τετραεκθετικού ανάλογα με το δείγμα και το μήκος κύματος ανίχνευσης. Το περίεργο χαρακτηριστικό του νέου μηχανισμού που ανιχνεύθηκε στα υμένια είναι ότι γίνεται πιο γρήγορος και πιο αποδοτικός καθώς το μήκος κύματος ανίχνευσης αυξάνει. Ένας παρόμοιος μηχανισμός δεν έχει αναφερθεί σε άλλες εργασίες με CIS/ZnS QDs, ενώ έχει αναφερθεί σε παλιότερες εργασίες με PbS QDs τόσο σε διαλύματα όσο και σε στερεά υμένια. Η μετατόπιση των πυκνών υμενίων προς το ερυθρό σε σχέση με τα αραιά αποτελεί ένδειξη της ύπαρξης μεταφοράς ενέργειας μεταξύ QDs διαφορετικών μεγεθών. / In this Master Thesis, the optical properties of CuInS2/ZnS nanocrystal quantum dots are investigated. For this purpose both steady state and time resolved spectroscopy, specifically the Time Correlated Single Photon Counting technique, were used. The photoluminescence properties of CuInS2/ZnS quantum dots, commonly known as CIS/ZnS QDs, either dissolved in solutions of different concentrations and solvent polarities or deposited on films made by spin-coating or drop-casting are studied. Either in the absorption and the photoluminescence steady state spectra, a red-shift both in the excitonic transition and the wavelength of the maximum intensity was observed as the concentration of the CIS/ZnS QDs or the polarity of the solvent increased. In films, a red-shifted photoluminescence spectrum is observed for films made by drop-casting compared to those prepared by spin-coating, having the same substrate material. By using time-resolved photoluminescence spectroscopy a three-exponential decay was observed in solutions, with time constants 1-3, 20-40 and 200-300 ns, while decays in films, apart from the three mechanisms also observed in solutions, also exhibit a fast decay component with a lifetime varying from some hundreds of ps until 4 ns. The attitude of the decay in films varies from two-exponential to four-exponential and it depends on the samples and the detection wavelength. The strange characteristic of the new mechanism which was detected in films is that its lifetime becomes shorter and its pre-exponential factor increases with the detection wavelength. To the best of our knowledge, such a faster decay as the emission wavelength increases has never been reported for CIS/ZnS QDs, but it has been reported for PbS QDs either diluted in solution or deposited in polymeric matrices. The time resolved photoluminescence spectra in the drop-casted films experience a larger transient red-shift than the spin-coated ones, indicative of a possible energy transfer among adjacent QDs with different diameters.