No description available.

The molecular design, synthesis and spectroscopic characterization of a series of ruthenium(II), metal-free and platinum(II) photosensitizers were discussed. The applications of some of these compounds in dye-sensitized solar were also outlined. To start with, a brief overview on the background of dye-sensitized solar cells (DSSCs) was presented in Chapter 1. In Chapter 2, a series of new thiocyanate-free ruthenium(II) cyclometalated complexes with different ligands were successfully synthesized and some of them were fully characterized by spectroscopic and computational methods. The nature of cyclometalating ligands effectively tunes the properties of the metal complexes and the resulting DSSC performance. In Chapter 3, new di-anchoring organic dyes have been synthesized and characterized. This molecular design strategy can significantly enhance the . value because this successfully inhibits the undesirable charge combination and prolongs the electron lifetime. The discoveries open up a new avenue to the evolution of organic sensitizers and the optimization of bridged di-anchoring dyes for highly efficient co-adsorbent-free DSSCs. In Chapter 4, a series of new thiophene-free platinum sensitizers for the application of DSSCs was developed. Four unsymmetrical platinum(II) di-acetylide complexes containing phenothiazine moiety with different donor units were designed and synthesized. These photosensitizers were fully characterized by spectroscopic as well as computational studies and also successfully employed in DSSC fabrication. These findings provided positive evidence that platinum-acetylide complexes have a great potential and prospect for the use as promising metal-based photosensitizers in DSSC applications. Finally, Chapters 5 and 6 present the concluding remarks and the experimental details of the work described in Chapters 2–4.

Στη παρούσα διπλωματική εργασία, μελετήθηκαν ευαισθητοποιημένες ηλεκτροχημικές ηλιακές κυψελίδες. Ιδιαίτερη έμφαση δόθηκε στη βελτιστοποίηση κύριων χαρακτηριστικών των κυψελίδων αυτών, όπως είναι η απόδοση και ο χρόνος ζωής των ηλεκτρονίων. Για το σκοπό αυτό, παρασκευάστηκαν ηλεκτροχημικές κυψελίδες οι οποίες περιείχαν λεπτά υμένια ημιαγωγού TiO2. Δοκιμάστηκαν διαφορετικά υλικά κατά τη σύνθεση της πάστας TiO2 (ΗNO3, CH3COCH2COCH3, H3PO4) καθώς και διαφορετικοί τρόποι παρασκευής των υμενίων αυτών (doctor blade, spin coating), με στόχο πάντα την επίτευξη υψηλότερης απόδοσης. Έγινε σύγκριση των αποτελεσμάτων έτσι ώστε να προσδιοριστούν οι διάφοροι παράγοντες στους οποίους οφείλονται τα προβλήματα στη λειτουργία των κυψελίδων αυτών. Για την ευαισθητοποίηση των παραπάνω υμενίων δοκιμάστηκε η χρωστική ρουθηνίου Ν3. Επίσης, στο αρχικό στάδιο των πειραμάτων, τα υμένια TiO2 των κυψελίδων χαρακτηρίστηκαν και ως προς τη μεταβατική φωτοαγωγιμότητά τους για μια επιπλέον ένδειξη της συμπεριφοράς τους στο κενό και στον αέρα. Η μέτρηση της μεταβατικής φωτοαγωγιμότητας έγινε, επίσης, και σε διαφορετικά πάχη υμενίων με στόχο τον καθορισμό του βέλτιστου πάχους. Δείγματα που περιείχαν HNO3 διαπιστώθηκε πως είχαν υψηλότερη απόδοση εν αντιθέσει με δείγματα που περιείχαν H3PO4 τα οποία είχαν χαμηλότερη απόδοση. Ο χρόνος ζωής ενός ηλεκτρονίου φαίνεται να διατηρείται σε υψηλά επίπεδα σε δείγματα που περιείχαν ΗΝΟ3, εν αντιθέσει με άλλα δείγματα στα οποία ο χρόνος ζωής είτε είχε ραγδαία μείωση εξαρχής (Η3PO4), ή είχε ασυνήθιστη μείωση και αύξηση στη δεύτερη και τρίτη μέτρηση (CH3COCH2COCH3). Η προσθήκη CH3COCH2COCH3 στην παρασκευή των υμενίων είχε ως αποτέλεσμα υμένια με υψηλότερη μεταβατική φωτοαγωγιμότητα τόσο στο κενό, όσο και στον αέρα, όμως, χωρίς ιδιαίτερη σταθερότητα. Αντίθετα, η προσθήκη HNO3 παρουσίασε ομαλότερη συμπεριφορά και σαφώς υψηλότερη μεταβατική φωτοαγωγιμότητα στα υμένια σε σύγκριση με υμένια που περιείχαν H3PO4, τα οποία ίσως και λόγω υψηλής ηλεκτραρνητικότητας της φωσφορικής ρίζας σε σύγκριση με αυτή της νιτρικής ρίζας, φάνηκαν ιδιαιτέρως ασθενή. Τα δείγματα παρουσίαζαν μείωση της απόδοσης σε συνάρτηση με το χρόνο. Επιπλέον, το γενικό συμπέρασμα για το πάχος ήταν πως πρέπει να κυμαίνεται γύρω στα 10μm για την αποδοτικότερη λειτουργία μιας ηλεκτροχημικής κυψελίδας. Το υμένιο τέτοιων κυψελίδων αποδείχτηκε πως έχει τη βέλτιστη μεταβατική φωτοαγωγιμότητα στο κενό και στον αέρα, επίσης. Επιπρόσθετα, η σύνδεση των ηλεκτροδίων ομοεπίπεδα (coplanar) σε σχέση με τη την σύνδεση τους ως σάντουιτς δίνει καλύτερα αποτελέσματα και μάλιστα με διαφορά μεγέθους τεσσάρων τάξεων, όσον αφορά τη μεταβατική φωτοαγωγιμότητα τόσο στο κενό, όσο και στον αέρα. Τέλος, η μέθοδος εναπόθεσης spin-coating ενδείκνυται για τα συγκεκριμένα πειράματα, λόγω επίτευξης υμενίων ιδιαιτέρως ομοιόμορφων και με επαναληψιμότητα. Λόγω επίτευξης μικρού πάχους υμενίων, ενδείκνυνται οι πολλαπλές επιστρώσεις για μεγαλύτερο πάχος των υμενίων. Συνίσταται, επίσης, εναλλακτικά είτε πυκνότερη πάστα, είτε λιγότερα δευτερόλεπτα περιστροφής, ή συνδυασμός αυτών των δύο παραμέτρων. Αντιθέτως, η μέθοδος doctor blade οδήγησε σε υμένια που δεν ήταν τόσο ομοιόμορφα και αυτό το γεγονός είχε αντίκτυπο και στη λειτουργία της κυψελίδας. / In the present thesis, dye-sensitized solar cells were studied. Particular emphasis was placed on optimizing the main characteristics of these cells, such as the efficiency and the lifetime of electrons. For this purpose, dye-sensitized solar cells were prepared containing thin films of semiconductor TiO2. Different materials were tested during the composition of the paste TiO2 (ΗNO3, CH3COCH2COCH3, H3PO4) as well as different ways of preparation of these films (doctor blade, spin coating), always aiming to achieve higher performance. Also, the results compared in order to identify individual factors behind the problems in the functioning of these cells. For the sensitization of these films, the ruthenium dye N3 was tested. Also, at the initial stage of the experiments, the TiO2 films of the cells were characterized in terms of their transient photoconductivity for an additional indication of the behavior in vacuum and in air. The measurement of the transient photoconductivity was taken place also at different film thicknesses in order to determine the optimal thickness. Samples containing HNO3 found to have higher performance unlike samples containing H3PO4 which had a lower performance. The lifetime of an electron appears to persist at high levels in samples containing HNO3, in contrast with other samples in which the lifetime was either rapidly reducing from the beginning (H3PO4), or had unusual decrease and increase in the second and third measurement (CH3COCH2COCH3). Adding CH3COCH2COCH3 in the preparation of the films had as a result films with higher transient photoconductivity both in vacuum and in air, but without particular stability. In contrast, the addition of HNO3 showed smoother behavior and clearly higher transient photoconductivity in films in comparison with films containing H3PO4, which perhaps due to the high electronegativity of phosphate in comparison with that of the nitrate anions, seemed particularly weak. The samples showed a reduction as a function of the time. Moreover, the overall conclusion for the thickness was that it should range around 10μm in order to achieve the most efficient operation of an electrochemical cell. It has proved that the film of such cells has the most optimum transient photoconductivity in vacuum and in air, too. Additionally, the coplanar way of connecting electrodes in relation with the “sandwich” way of connecting electrodes gives better results, with difference of four grades size concerning the transient photoconductivity both in vacuum and in air. Finally, the method of spin-coating deposition is indicated for these experiments, achieving films particularly uniform and highly reproducible. Since films are thin, multiple coatings are appropriate for thicker films. Also, it is recommended, alternatively, either denser paste or fewer seconds of rotation, or a combination of these two parameters. In contrast, doctor blade method leaded to films that are not uniform at all and this fact had an impact on the function of the cell.

published_or_final_version / Physics / Doctoral / Doctor of Philosophy

No description available.

This thesis focuses on liquid redox electrolytes in dye-sensitized solar cells (DSCs). A liquid redox electrolyte, as one of the key constituents in DSCs, typically consists of a redox mediator, additives and a solvent. This thesis work concerns all these three aspects of liquid electrolytes, aiming through fundamental insights to enhance the photovoltaic performances of liquid DSCs. Initial attention has been paid to the iodine concentration effects in ionic liquid (IL)-based electrolytes. It has been revealed that the higher iodine concentration required in IL-based electrolytes can be attributed to both triiodide mobility associated with the high viscosity of the IL, and chemical availability of triiodide. The concept of incompletely solvated ionic liquids (ISILs) has been introduced as a new type of electrolyte solvent for DSCs. It has been found that the photovoltaic performance of ISIL-based electrolytes can even rival that of organic solvent-based electrolytes. And most strikingly, ISIL-based electrolytes provide highly stable DSC devices under light-soaking conditions, as a result of the substantially lower vapor pressure of the ISIL system. A significant synergistic effect has been observed when both guanidinium thiocyanate and N-methylbenzimidazole are employed together in an IL-based electrolyte, exhibiting an optimal overall conversion efficiency. Tetrathiafulvalene (TTF) has been investigated as an organic iodine-free redox couple in electrolytes for DSCs. An unexpected worse performance has been observed for the TTF system, albeit it possesses a particularly attractive positive redox potential. An organic, iodine-free thiolate/disulfide system has also been adopted as a redox couple in electrolytes for organic DSCs. An impressive efficiency of 6.0% has successfully been achieved by using this thiolate/disulfide redox couple in combination with a poly (3, 4-ethylenedioxythiophene) (PEDOT) counter electrode material under full sunlight illumination (AM 1.5G, 100 mW/cm2). Such high efficiency can even rival that of its counterpart DSC using a state-of-the-art iodine-based electrolyte in the systems studied.The cation effects of lithium, sodium and guanidinium ions in liquid electrolytes for DSCs have been scrutinized. The selection of the type of cations has been found to exert quite different impacts on the conduction band edge (CB) of the TiO2 and also on the electron recombination kinetics, therefore resulting in different photovoltaic behavior. / QC 20120124

The thesis discusses how to utilize Sol-gel method to prepare nano-sized TiO2 films of photoelectrodes and the their use in Dye-Sensitized Solar Cells. The main goal is the study on the production of TiO2 photoelectrodes. When making nano-sized TiO2 films of photoelectrodes, we have to first produce TiO2 sol via the Sol-gel method optical thin films are then made by spin coating. After its spin coating, we study the crystalline phase and morphology of nano-sized TiO2 films of photoelectrodes in terms of two ways: Supercritical drying and oven drying. Among the Dye-Sensitized Solar Cells that are made with different drying methods, owing to higher porosity and surface area, the nano-sized TiO2 films of photoelectrodes made by supercritical drying adsorb more dye molecules and are thus more efficient.

<p>This thesis is divided into four parts with organic chromophores for dye sensitized solar cells as the common feature and an introduction with general concepts of the dye sensitized solar cells.</p><p>The first part of the thesis describes the development of an efficient organic chromophore for dye sensitized solar cells. The chromophore consists of a triphenylamine moiety as an electron donor, a conjugated linker with a thiophene moiety and cyanoacrylic acid as an electron acceptor and anchoring group. During this work a strategy to obtain an efficient sensitizer was developed. Alternating the donor, linker or acceptor moieties independently, would give us the tool to tune the HOMO and LUMO energy levels of the chromophores. The following parts of this thesis regard this development strategy.</p><p>The second part describes the contributions to the HOMO and LUMO energy levels when alternating the linker moiety. By varying the linker the HOMO and LUMO energy levels was indeed shifted. Unexpected effects of the solar cell performances when increasing the linker length were revealed, however.</p><p>The third part describes the investigation of an alternative acceptor group, rhodanine-3-acetic acid, in combination with different linker lengths. The HOMO and LUMO energy level tuning was once again successfully shifted. The poor electronic coupling of the acceptor group to the semiconductor surface proved to be a problem for the overall efficiency of the solar cell, however.</p><p>The fourth part describes the contributions from different donor groups to the HOMO and LUMO energy levels and has so far been the most successful in terms of reaching high efficiencies in the solar cell. A top overall efficiency of 7.1 % was achieved.</p>

Thesis (Ph.D.)--Bowling Green State University, 2009. / Document formatted into pages; contains xix, 184 p. : ill. Includes bibliographical references.

Thesis (Ph. D.)--University of Washington, 2003. / Vita. Includes bibliographical references (p. 76-82).