Στα πλαίσια της παρούσας διδακτορικής διατριβής μελετήθηκαν και αναπτύχθηκαν νανοδομημένα λεπτά υμένια διοξειδίου του τιτανίου (TiO2) και λευκόχρυσου (Pt) για χρήση σε ευαισθητοποιημένες φωτοβολταϊκές κυψελίδες. Αφού πραγματοποιήθηκε η μελέτη των υμενίων, παρασκευάστηκαν υμένια TiO2 και Pt και βελτιστοποιήθηκαν, ώστε να έχουν τις επιθυμητές ιδιότητες. Για το χαρακτηρισμό των υμενίων TiO2 χρησιμοποιήθηκε ηλεκτρονικό μικροσκόπιο σάρωσης (SEM) και περίθλαση ακτίνων X (XRD). Μάλιστα προτάθηκε η χρήση νιτρικού οξέος, ανάμεσα σε 4 διαφορετικά οξέα, για την αποτελεσματική διασπορά των σωματιδίων του TiO2 και την παρασκευή ομοιόμορφων υμενίων, χωρίς την παρουσία ρωγμών και με πάχος πάνω από 10 μm. Τα υμένια που παρασκευάστηκαν χρησιμοποιήθηκαν σε ευαισθητοποιημένες φ/β κυψελίδες και μελετήθηκε η επίδραση της δομής τους στην απόδοση των κυψελίδων. Για τα υμένια Pt αναπτύχθηκαν δυο διαφορετικοί τρόποι παρασκευής (θερμική διάσπαση αλάτων Pt, ηλεκτροαπόθεση). Τα υμένια που προέκυψαν αξιολογήθηκαν με βάση τη μορφολογία και τις καταλυτικές τους ιδιότητες ως προς την αναγωγή των ιόντων τριωδίου και προτάθηκαν τρόποι για τη βελτιστοποίησή τους. Ιδιαίτερη βαρύτητα δόθηκε στη σταθερότητα των υμενίων Pt κατά την παραμονή τους σε διάλυμα ηλεκτρολύτη, ίδιο με αυτό που χρησιμοποιείται στις ευαισθητοποιημένες κυψελίδες. Τέλος τα υμένια TiO2 και Pt ενσωματώθηκαν σε πρότυπες φωτοηλεκτροχρωμικές διατάξεις, στις οποίες η ενέργεια που απαιτείται για τη μεταβολή της διαπερατότητάς τους παρέχεται από την ενσωματωμένη φ/β κυψελίδα. Μάλιστα προτάθηκε και μελετήθηκε ένας νέος τύπος διάταξης. / In this PhD thesis we have studied and prepared nanostructured titanium dioxide (TiO2) and platinum (Pt) thin films, in order to use them for dye sensitized solar cells. The morphology and the structure of the TiO2 films were examined with scanning electron microscopy (SEM) and x-ray diffraction (XRD). We have proposed the use of nitric acid, among four other acids, in order to achieve a more efficient dispersion of TiO2 nanoparticles and to prepare uniform and crack free films, with thickness above 10 μm. The TiO2 films were used in dye sensitized solar cells and was examined the relation between the structure of the films and the efficiency of the cells. For the deposition of Pt films we have used two different methods (thermal decomposition of Pt salts and electrodeposition). The films were characterized according to their morphology and their catalytic activity towards triiodide ions reduction. Moreover we have proposed methods for improving the properties of Pt films and we have studied their stability, especially when the films were stored in the same electrolyte solution as that in dye sensitized solar cells. Finally the TiO2 and Pt films were used in photoelectrochromic devices, where the energy produced by the photovoltaic cell is used for the modulation of device’s transmittance. Also a new type of a photoelectrochromic device was introduced and studied.

<p> In an era of advancing printed electronics, solution-processable organic semiconductors continue to make significant strides in electronic and optoelectronic applications. Electrochromic (EC) technology, which encompass reversible optical modulation under electrochemical biasing, has progressed rapidly over the past half-century and developed into niche commercial-scale devices for auto-tinting glasses as well as low-power, non-emissive displays. To utilize the advantages of organic electrochromic materials in next-generation devices, it is imperative to understand their fundamental material properties, interactions with other device components, and the underlying electrochemistry that governs the overall optical and electrochemical response of the complete electrochromic device. This dissertation presents a discussion on the synergistic role of organic electrochromes, charge-balancing layers and electrolytes in determining two key performance metrics, namely the optical contrast and operational stability, of an electrochromic device (ECD). The absorption features of colored-to-transmissive switching conjugated polymers have been investigated by exploring material design strategies in conjunction with analytical approaches to optimize and enhance the optical contrast. In parallel, transmissive redox-active radical polymer counter electrodes have been developed as compatible charge-balancing layers and integrated into devices by pairing with electrochromic polymers (ECPs) to achieve stable and high-contrast optical modulation. Electrochemical activity of both conjugated and radical polymer electrodes in different ionic and solvent environments have been further examined to understand material-electrolyte interactions governing mixed ionic-electronic conduction. Finally, a small molecular approach to realizing transparent-to-colored electrochromism is discussed, where distinct substituent-induced degradation pathways of conjugated radical cations were revealed. Overall, this research aims to assist future development of robust, ultra-high contrast organic electrochromic platforms.  </p>

Dye-sensitized solar cells (DSC) have attracted considerable scientific and industrial interest during the past decade as an economically feasible alternative to conventional photovoltaic devices. DSCs have the potential to be as efficient as silicon solar cells, but at a fraction of the cost of silicon solar cells. The unique advantage of DSC compared to conventional solar cells is that the light absorption, electron transport and hole transport are handled by different components which reduces the chance of recombination. In the present work, to facilitate DSC with good energy conversion efficiency, its performance have been evaluated as a function of titania layer morphology, redox couple concentration and the catalytic layer on the counter electrode. The results that are obtained in the present investigations have been organized as follows Chapter 1 gives a brief exposure to DSC technology. Special emphasize has been on the structure and individual components of the DSC. Chapter 2 describes various experimental techniques that are employed to fabricate and characterize DSCs under study. Chapter 3 presents a systematic study of the characteristics of DSC made of three different types of electrodes namely: TiO2 nanotubes (TNT) which have excellent electron transport properties, TiO2 microspheres (TMS) which possess high surface area and light scattering ability and TiO2 nano particles (TNP) possessing high surface area. The electronic, morphological, optical and surface properties of individual electrodes are studied. The highest efficiency of 8.03% is obtained for DSCs prepared with TMS electrodes. A higher value of effective diffusion coefficient (Deff) and diffusion length (Ln) of electrons as obtained by electrochemical impedance spectroscopy (EIS) analysis confirms a high charge collection efficiency in microsphere based cell. Chapter 4 gives a detailed study of DSCs fabricated with a tri-layer photo anode with TNTs as light scattering layer. The tri-layer structure has given an enhanced efficiency of 7.15% which is 16% higher than TNP based cell and 40% higher than TNT based cells. Chapter 5 deals with the investigations on the effect of concentration of redox couple on the photovoltaic properties of DSC for different ratios of [I2] to [LiI] (1:2, 1:5 and 1:10) with five viii concentrations of I2 namely 0.01 M, 0.03 M, 0.05 M, 0.08 M and 0.1M in acetonitrile. It is found that the open circuit potential (Voc) decreases with increase in the ratio of redox couple whereas short circuit current density (Jsc) and fill factor (FF) increase. The reason for the decline in Voc is the higher recombination between electrons in the conduction band of TiO2 and the I3- ions present in the electrolyte, induced by the absorptive Li+ ions. In addition using EIS it is found that the τ improves with the increase in [LiI] at a particular [I2], whereas at a fixed [I2]/ [LiI] ratio the increase in [I2] is found to reduce the τ and Deff due to the enhanced recombination. Chapter 6 describes the application of carbon based counter electrode (CE) materials for DSCs. Two counter electrode materials have been investigated namely (1) Multiwalled carbon nanotubes (MWCNT) synthesized by pyrolysis method and (2) Platinum decorated multiwalled carbon nanotubes (Pt/MWCNT) prepared by chemical reduction of platinum precursors. Using Pt/MWCNT composite electrode the DSC achieved an energy conversion efficiency of 6.5 %. From the analysis on symmetric cells, it is found that electro catalytic activity of Pt/MWCNT CE is similar to that of platinum CE, though the platinum loading is very less for the former. This is attributed to the effective utilization of catalyst owing to high surface area arising from the increased surface roughness. Chapter 7 discusses the application of titanium foil in place of glass substrate for the photo anode. The titanium foil offers fabrication of flexible DSC. The performance of DSC with TMS layers and aligned titania nanotube arrays (TNA) prepared by anodization method is studied. Compared to TMS based cell, TNA has given a better efficiency at a lower thickness. Chapter 8 presents the scheme used to seal DSCs and its stability analysis. We have employed the usual hot melt sealing for edge whereas hole sealing is carried out with tooth pick and a UV curable adhesive. The degradation in efficiency is found to be 20% for low efficiency cells whereas, for high efficiency cells it is found to be 45% after 45 days. The leakage of highly volatile acetonitrile through the edge and hole is found to be responsible for the reduction in the performance of the device. Hence a high temperature sealing method is proposed to fabricate stable cells. Chapter 9 gives summary and conclusions of the present work