<p>Dye-sensitised solar cells (DSC) have attracted much attention during the last few years due to their high efficiencies and their potentially low production costs. The technology is based on a thin layer of nano sized, high band gap (3.2 eV) TiO2 film. A Ru containing dye (from hereon called the Ru dye) is chemisorbed onto the TiO2 film. This combination acts as the working electrode. The counter electrode consists of a platinum layer which is the catalyst for the regeneration of the Iodine/Iodide electrolyte. The work that is presented here is focused on the results that were obtained during studies of the performance of the DSC under certain reverse bias conditions. When one cell in the series connection in a module is shaded, the current will pass this cell in reverse bias. In such a case the shaded cell will be subjected to a voltage in the reverse direction coming from the other lit cells in the module. This reverse voltage could permanently modify or damage the cell if it is not properly protected. Although the work is focussed on the chemical stability of the dye, various techniques were employed to determine the physical changes in the cell. It was found that a cell that was subjected to a reverse bias of 2 V for 500 min showed a 58% recovery and a cell that was subjected to 4.5 V reverse bias was irreversibly damaged. The UV-vis spectra showed a blue shift (higher energy), the Raman showed no peak at 1713 cm-1 (which indicates the absence of free carboxylate groups) and the FT-IR showed the disappearance of the NC-S absorption band at 2100 cm-1. The combined conclusion is that the &ndash / NCS ligand has been depleted and replaced with I3- ions. When measuring the impedance, the Nyquist plots showed an increase in the charge transfer resistance at the counter electrode when subjected to a reverse bias potential of 2 V. This is confirmed by the Bode plots. This indicates a partial oxidation of the Pt catalyst on the counter electrode. It can therefore be stated with confidence that the changes in the cell after being subjected to a reverse bias potential of 2 V for 500 min are changes on the -NCS bonds on the Ru dye as well as the Pt in the counter electrode.</p>

<p>Dye-sensitised solar cells (DSC) have attracted much attention during the last few years due to their high efficiencies and their potentially low production costs. The technology is based on a thin layer of nano sized, high band gap (3.2 eV) TiO2 film. A Ru containing dye (from hereon called the Ru dye) is chemisorbed onto the TiO2 film. This combination acts as the working electrode. The counter electrode consists of a platinum layer which is the catalyst for the regeneration of the Iodine/Iodide electrolyte. The work that is presented here is focused on the results that were obtained during studies of the performance of the DSC under certain reverse bias conditions. When one cell in the series connection in a module is shaded, the current will pass this cell in reverse bias. In such a case the shaded cell will be subjected to a voltage in the reverse direction coming from the other lit cells in the module. This reverse voltage could permanently modify or damage the cell if it is not properly protected. Although the work is focussed on the chemical stability of the dye, various techniques were employed to determine the physical changes in the cell. It was found that a cell that was subjected to a reverse bias of 2 V for 500 min showed a 58% recovery and a cell that was subjected to 4.5 V reverse bias was irreversibly damaged. The UV-vis spectra showed a blue shift (higher energy), the Raman showed no peak at 1713 cm-1 (which indicates the absence of free carboxylate groups) and the FT-IR showed the disappearance of the NC-S absorption band at 2100 cm-1. The combined conclusion is that the &ndash / NCS ligand has been depleted and replaced with I3- ions. When measuring the impedance, the Nyquist plots showed an increase in the charge transfer resistance at the counter electrode when subjected to a reverse bias potential of 2 V. This is confirmed by the Bode plots. This indicates a partial oxidation of the Pt catalyst on the counter electrode. It can therefore be stated with confidence that the changes in the cell after being subjected to a reverse bias potential of 2 V for 500 min are changes on the -NCS bonds on the Ru dye as well as the Pt in the counter electrode.</p>

Philosophiae Doctor - PhD / Dye-sensitised solar cells (DSC) have attracted much attention during the last few years due to their high efficiencies and their potentially low production costs. The technology is based on a thin layer of nano sized, high band gap (3.2 eV) TiO2 film. A Ru containing dye (from hereon called the Ru dye) is chemisorbed onto the TiO2 film. This combination acts as the working electrode. The counter electrode consists of a platinum layer which is the catalyst for the regeneration of the Iodine/Iodide electrolyte. The work that is presented here is focused on the results that were obtained during studies of the performance of the DSC under certain reverse bias conditions. When one cell in the series connection in a module is shaded, the current will pass this cell in reverse bias. In such a case the shaded cell will be subjected to a voltage in the reverse direction coming from the other lit cells in the module. This reverse voltage could permanently modify or damage the cell if it is not properly protected. Although the work is focussed on the chemical stability of the dye, various techniques were employed to determine the physical changes in the cell. It was found that a cell that was subjected to a reverse bias of 2 V for 500 min showed a 58% recovery and a cell that was subjected to 4.5 V reverse bias was irreversibly damaged. The UV-vis spectra showed a blue shift (higher energy), the Raman showed no peak at 1713 cm-1 (which indicates the absence of free carboxylate groups) and the FT-IR showed the disappearance of the NC-S absorption band at 2100 cm-1. The combined conclusion is that the - NCS ligand has been depleted and replaced with I3- ions. When measuring the impedance, the Nyquist plots showed an increase in the charge transfer resistance at the counter electrode when subjected to a reverse bias potential of 2 V. This is confirmed by the Bode plots. This indicates a partial oxidation of the Pt catalyst on the counter electrode. It can therefore be stated with confidence that the changes in the cell after being subjected to a reverse bias potential of 2 V for 500 min are changes on the -NCS bonds on the Ru dye as well as the Pt in the counter electrode. / South Africa

Orientadores: Vitor Baranauskas, Helder José Ceragioli / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia Elétrica e de Computação / Made available in DSpace on 2018-08-27T01:34:46Z (GMT). No. of bitstreams: 1 Silva_ThiagoFranchiPereirada_D.pdf: 9373432 bytes, checksum: 13a36b35d789088396a134f65246b3a9 (MD5) Previous issue date: 2015 / Resumo: Células solares orgânicas e inorgânicas representam uma excelente alternativa como fonte de energia renovável. Este trabalho consiste em aplicar nanoestruturas de carbono obtidas pela técnica HFCVD (Hot Filament Chemical Vapour Deposition) como componentes utilizados na construção e melhoria de células solares orgânicas (organic photovoltaics - OPVs) e células sensibilizadas por corante (dye-sensitized cells - DSCs). Foi obtido óxido de grafeno reduzido (rGO), carbono tipo diamante (DLC - diamondlike carbon) e diamante condutor nanoestruturado. Estes materiais foram caracterizados por microscopia eletrônica de varredura (SEM-FEG), microscopia de transmissão de alta resolução (HRTEM), espectroscopia Raman e análise termogravimétrica (TGA). O rGO foi empregado na construção das células DSC misturado na pasta de TiO2 em diferentes concentrações, produzindo o aumento de fotocorrente gerada e, consequentemente, o rendimento. O mesmo material foi empregado nas OPVs, em diferentes concentrações, para a substituição do fulereno PCBM (1-(3-metoxicarbonil)-propil-1-1-fenil- (6,6)metanofulereno) e também em conjunto com o fulereno, sendo observada também a melhoria no desempenho dos dispositivos em função da concentração. Com finalidade de substituir os contraeletrodos das células DSC, carbono tipo diamante foi depositado em substrato de alumínio (Al) e diamante condutor nanoestruturado depositado em substratos de nióbio (Nb). As células com contraeletrodos de Al com filme de DLC apresentaram sensibilidade à luz, com possibilidade de aplicação em sensores ópticos, enquanto as células com contraeletrodos de Nb com filme de diamante condutor apresentaram excelente desempenho, tornando possível a substituição dos contraeletrodos de platina / Abstract: Organic and inorganic solar cells comprise a promising solution as a renewable energy source. This work consists of applying carbon nanostructures obtained by HFCVD technique (Hot Filament Chemical Vapour Deposition) as components used in the construction and improvement of organic solar cells (organic photovoltaics - OPVs) and dye sensitized cells (dye-sensitized cells - DSCs). Reduced graphene oxide (rGO), carbon diamond-like (DLC - diamond- like carbon) and nanostructured conductor diamond was obtained. These materials were characterized by scanning electron microscopy (SEM-FEG), high resolution transmission microscopy (HRTEM), Raman spectroscopy and thermal gravimetric analysis (TGA). Reduced graphene oxide was used for the construction of the DSC cell at the TiO2 layer mixed in different concentrations, producing an increase in photocurrent generated and thus conversion efficiency. The same material was used in the OPVs at different concentrations for the replacement of fullerene PCBM (1- (3-methoxycarbonyl) -propyl-1-1-phenyl- (6,6) metanofulereno) and with the fullerene was also observed improvement in performance of the devices as a function of concentration. With aim of replacing the counterelectrode of DSCs cells, diamond-like carbon was deposited on aluminum substrate (Al) and nanostructured conductive diamond deposited on niobium (Nb) substrates. Cells with Al/DLC counterelectrode showed sensitivity to light, with the possibility of application in optical devices while cells with Nb/nanostructured conductive diamond counterelectrode showed excellent performance, with possibility to replace platinum counterelectrodes / Doutorado / Eletrônica, Microeletrônica e Optoeletrônica / Doutor em Engenharia Elétrica

The main focus of this thesis is ab initio modeling of core level spectra with a high-level quantum chemical description both of the chemical interactions and of local atomic multiplet effects. In particular, the combination of calculations and synchrotron-based core-level spectroscopy aims at understanding the local structure of the electronic valence in transition metal complexes, and the details of the solvation mechanisms of electrolyte solutions, systems relevant for the dye-sensitized solar cell. Configurational sampling in solution is included through molecular dynamics simulations. Transition metal complexes are studied with x-ray absorption (XA) and resonant inelastic scattering (RIXS) spectroscopy, characterizing excited states with atomic site specificity. The theoretical multiconfigurational method, applying an active-space partitioning of the molecular orbitals (RASSCF), is used to assign the transitions observed in spectra of hydrated Ni2+ explicitly, including charge transfer and multiplet effects. Furthermore, the solvent-induced binding energy properties of the I- and I3- anions in aqueous, ethanol, and acetonitrile solutions are analyzed using photoelectron spectroscopy (XPS). The study shows that specific ion–solvent interactions are important for the core-level binding energy shifts in solution. The special case with I3- dissolved in water, where hydrogen bonding causes breaking of the molecular symmetry, is treated and proves that the geometry changes influence the photoelectron spectrum of aqueous I3- directly.

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