Orientador: Maria Aparecida Zaghete Bertochi / Banca: Talita Mazon / Banca: Fenelon Martinho Lima Pontes / Banca: Luiz Vicente de Andrade Scalvi / Banca: Claudia longo / O Programa de Pós Graduação em Ciência e Tecnologia de Materiais, PosMat, tem caráter institucional e integra as atividades de pesquisa em materais de diversos campi / Resumo: O desenvolvimento das células solares de perovskita foi acompanhado por uma revolução no campo dos dispositivos fotovoltaicos. Células solares de perovskita atingiram eficiências de conversão de energia maiores que 21% em apenas 5 anos após sua descoberta, colocando-as em competição com as células solares comerciais de silício. Apesar de promissores, os dispositivos de perovskita enfrentam desafios que impedem sua comercialização, sendo o maior deles o problema de estabilidade. Nesse âmbito, a presente tese teve como principal foco o desenvolvimento de células solares de perovskita baseadas em filmes nanoestruturados de Nb2O5 e TiO2, visando melhor compreensão do funcionamento desses dispositivos afim de se obter a solução dos problemas hoje enfrentados. Os resultados obtidos mostram eficiências maiores que 13% para o sistema: filme compacto de Nb2O5/ filme mesoporoso de TiO2/ CH3NH3PbI3; e eficiências tão elevadas quanto 15% para sistema usando filme compacto e mesoporoso de TiO2/ CH3NH3PbI3. As melhores células solares montadas com filmes compactos de Nb2O5 apresentaram correntes de curto circuito de 19 mA/cm2, tensão de circuito aberto de 960 mV, fator de preenchimento de 75% e eficiências de 13%. Para as células formadas com filmes de compactos de TiO2 foram obtidas correntes de curto circuito de 20 mA/cm2, tensão de circuito aberto de 1V, fator de preenchimento de 70% e eficiências de 15%. A estabilidade dos dispositivos e a presença de histerese nas curvas de tensão-cor... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: The development of perovskite solar cells was accompanied by a revolution in the photovoltaics field. Perovskite solar cells have reached higher energy conversion efficiencies of 21% in just 5 years after its discovery, putting them in competition with commercial silicon solar cells. Although promising, the perovskite devices face some challenges which delay their commercialization, and one of most important is the stability. In this context, the present thesis intended the development of perovskite solar cells based on nanostructured films of Nb2O5 and TiO2, in order to better understand the functioning of these devices. Efficiencies up to 13% were obtained for the system composed of: compact Nb2O5 / mesoporous TiO2/ CH3NH3PbI3 and efficiencies as high as 15% for compact system using compact TiO2/ mesoporous TiO2/ CH3NH3PbI3. The best solar cells prepared using compact Nb2O5 films showed a short circuit current of 19 mA/cm 2, open circuit voltage of 900 mV, fill factor of 75% and 13% of efficiency. Devices prepared using compact TiO2 films reached short circuit current of 20 mA/cm2, open circuit voltage of 1V, fill factor of 70% and 15% of efficiency. The stability of the devices and the presence of current-voltage hysteresis were studied by changing parameters such as the composition and the thickness of the compact layer (TiO2 vs. Nb2O5), as well as the synthesis method used to prepare the perovskite films (sequential deposition method vs solvent-engineering method). Ove... (Complete abstract click electronic access below) / Doutor

Orientador: Carlos Frederico e Oliveira Graeff / Banca: André Sarto Polo / Banca: Fenelon Martinho Lima Pontes / Banca: Francisco das Chagas Marques / Banca: José Humberto Dias da Silva / Resumo: Este projeto consiste na produção e estudo das propriedades de novos materiais para a otimização de células solares sensibilizadas por corante (DSSC) baseadas em filmes de TiO2 nanoestruturado e corantes da família do N3. A pesquisa foi focada no estudo e na otimização de novos contra elétrodos baseados em CuS e CoS nanoestruturados, os quais apresentam grande interesse no setor de pesquisa e desenvolvimento industrial, pelas suas promissoras características eletrocatalíticas e pelos seus baixos custos. Além da obtenção das nanopartículas de CuS e CoS pela técnica hidrotermal assistida por micro-ondas, um grande esforço foi feito a fim de obter tintas precursoras ideais para a deposição dos filmes de CuS e CoS pela técnica de screen-printing, compatível com as modernas linhas de produção industriais. Portanto, foram desenvolvidos e otimizados métodos simples, rápidos e de baixo custo para obter filmes finos dos materiais estudados. Em particular tivemos um grande sucesso utilizando a estratégia do precursor químico dissolvido em solventes. Na primeira aplicação deste método, um precursor químico (Co(II) dietilditiocarbamato) foi utilizado em tintas à base de CH2Cl2. Foram obtidos elétrodos de CoS nanocristalinos e de alta eficiência. Todavia o uso do solvente orgânico clorado não é muito apropriado para grandes superfícies. Portanto, desenvolvemos um método baseado num precursor químico do CoS hidrossolúvel e de baixa toxidade. Com este método aprimorado foram obtidos bons re... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: This project consists of the production and study of new materials for the optimization of dye-sensitized solar cells (DSSC) based on nanostructured TiO2. The research was focused on the design and optimization of new counter electrodes based on CuS and CoS nanoparticles, which are very interesting in the research and development of DSSC, due to their promising electrochemical characteristics and for their lower costs. Along with the hydrothermal technique assisted by microwave, a great effort was made to obtain optimum precursor inks for deposition of CuS and CoS films by screen-printing technique, compatible with modern industrial production lines. Hereby facile, inexpensive and rapid methods for thin films have been developed and optimized for the deposition of CuS and CoS layers. In particular, we developed a chemical precursor process using solvent-based inks. In the first application of this approach, a chemical precursor CoS (Co (II) diethyldithiocarbamate) was used in CH2Cl2. Nanocrystalline CoS electrodes and high efficiency have been obtained, however the use of chlorinated organic solvent is not very suitable for large surfaces. Therefore, we developed a method based on a water-soluble (WS) chemical precursor. Good results have been obtained, in terms of stability and efficiency, with the WS precursor. The counter electrode developed with our methods were tested with alternative redox pairs such as Co2+/Co3+ and ferrocene. Such an application of CuS and CoS electro... (Complete abstract click electronic access below) / Mestre

In 2017, 98 gigawatts of solar capacity were added globally, outpacing new contributions from coal, gas and nuclear plants combined, based on 161 billion dollars of investment. Solar is the leading contributor to the clean energy revolution and continues to grow in market share and drop in price every year as economy of scale advances the technology. Within this market, silicon and cadmium telluride solar cells dominate nearly all of market share, converting roughly 20% of incident solar power into electricity. It is worth noting that the gains from a 1% increase in power conversion efficiency of the typical 20% solar cell to 21% would be measured, annually, in billions of dollars. If the solar cells installed last year had 1% more power conversion efficiency and the power displaced coal power generation, this enhancement in efficiency would now save roughly 8,000,000 pounds of carbon dioxide emission per hour every hour for the ~220,000-hour (~25 year) lifetime of the solar cells. Within this context, enhancing the power conversion efficiency of solar cells is crucial economically and environmentally. Because sunlight is incident on the earth as a broad spectrum of different colors, the energy of the photons spans a wide range. Unfortunately, the spectral range limits power conversion efficiency. For example, solar cells are transparent to photons with insufficient energy, while photons with excess energy relax to the band edge of the solar material, losing the excess energy as heat. This thesis focuses on improving the utilization of high energy photons currently lost to this thermalization process. In Chapter 1, we introduce the photophysical process of singlet exciton fission and give an overview of the field, with a focus on its potential for incorporation into photovoltaic devices. In Chapter 2-8, we discuss our results realizing singlet exciton fission in molecular systems, specifically bipentacenes. This chapter includes the synthesis of these materials, theoretical calculations predicting and rationalizing their photophysical behavior, and the spectroscopic characterization used to demonstrate the singlet fission process. In Chapter 3, we detail a modular synthetic approach to oligomers and even the first polymer of pentacene. We also discuss some basic properties of these materials using techniques such as linear absorption, cyclic voltammetry, and grazing incidence wide angle X-ray scattering spectroscopy. In Chapter 4, we investigate the photophysics of these materials. Photoluminescence upconversion spectroscopy reveals the decay of the singlet exciton on ultrafast timescales, while transient absorption spectroscopy is used to assign the singlet fission timescale, as well as to characterize the triplet absorption spectra. Chapter 5 discusses the synthesis and photophysics of homoconjugated and non-conjugated pentacene dimers, where singlet fission occurs through sigma bonds. Again, transient absorption spectroscopy is crucial to the assignment of the photophysics at play, but continuous wave time resolved electron spin resonance measurements yield additional insights into interaction between the resulting triplet pair excitons. Chapter 6 provides further detail into the formation of strongly exchange coupled triplet pair states. Continuous wave time resolved electron spin resonance spectroscopy is used to determine the quintet character of these states, and pulsed electron spin resonance measurements nutate the spin of these states to confirm this assignment. Chapter 7 provides the first demonstration that singlet exciton fission is also possible in heterodimer systems. Finally, Chapter 8 delves more deeply into the exciton correlations in these materials with a special focus on the pentacene-tetracene dimer system.

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Polymer solar cells (PSCs) are one of the cost-effective alternatives to the traditional silicon-based solar cell. To be commercially viable, a number of its shortfalls have to be addressed. First, the charge mobility and life time of the organic materials used in PSCs are low and results in a large series resistance and inefficient charge separation. Second, the range of absorption of light in PSCs is not wide enough to cover the whole solar spectrum. Hence, the highest power conversion efficiency (PCE) achieved by PSCs is still low compare to other types of solar cells. In this thesis, several methods were investigated to improve the PCE of PSCs base on the donor polymer Poly(3-hexylthiophene-2,5-diyl) (P3HT) and acceptor fullerene Phenyl-C61-butyric acid methyl ester (PCBM). It was found to be essential to control the drying rate of the solvent after spin-coating the polymer solution on a piece of glass as it would affect the ordering and crystallinity of the polymer chains. Besides, instead of a bulk heterojuction (BHJ) structure, a bilayer device can also give a comparable PCE by spin-coating P3HT and PCBM separately using orthogonal solvents. Factors that could affect the performance of bilayer devices, such as the drying rate and thermal annealing, were investigated. It was found that thermal annealing is essential since it would facilitate the interdiffusion of the two layers. In order to improve the range of spectral absorption of light, a squaraine dye was introduced. Squaraine has a high absorbance in the near-infrared range where the absorption is poor for P3HT. The PCE was found to increase by about 5 % by incorporating 0.5 wt % of squaraine into the BHJ system. In addition, squaraine was introduced to the bilayer system. It was found that the performance was slightly improved when squaraine was blended with PCBM in the upper layer. Various parameters were tuned to optimize the performance of this bilayer system. / 聚合物太陽能電池是其中一個比傳統晶體矽太陽能電池有更高成本效益的代替品。然而，聚合物太陽能電池仍然有若干缺點需要解決才能夠成為商業市場上流通的產品。首先，聚合物太陽能電池所使用的有機材料的電荷遷移率和壽命低，造成較大的串聯電阻和低效率的電荷分離。其次，聚合物太陽能電池的吸收光譜範圍較窄，不足以覆蓋整個太陽光譜。因此，相比起其他類型的太陽能電池，聚合物太陽能電池的最高能量轉換效率仍然偏低。在本論文中，我們建基於供體P3HT和受體PCBM' 進行了多分面的研究。我們發現旋塗聚合物溶液後，控制溶劑的乾燥速度是很重要的，因為這會影響聚合物鏈的排序和結晶度。另外，除了體異質接面結構外，利用正交溶劑來分別旋塗P3HT和PCBM的雙層結構亦可得到可比的最高能量轉換效率。我們研究了數個可能影響雙層結構聚合物太陽能電池效能的因素，例如乾燥速度和熱退火處理，並發現熱退火處理是非常重要，因為熱退火可以有利於兩層聚合物的相互擴散。為了擴闊電池的吸收光譜範圍，我們引入了方酸染料。方酸在近紅外線範圍內具有高的吸光率，而在此範圍內P3HT的吸光率都欠佳。在慘雜0.5重量百分比的方酸到原有的體異質接面結構後，最高能量轉換效率提升了大約百分之五。此外，方酸也才參雜到雙層結構系統內，結果發現，當方酸慘雜在上層中的PCBM後，電池的效能稍有改善。我們調整了各種參數，以完善該雙層系統的效能。 / Chow, Chun Yin = 雙層及摻雜染料聚合物太陽能電池研究 / 周俊然. / Thesis M.Phil. Chinese University of Hong Kong 2015. / Includes bibliographical references (leaves 90-92). / Abstracts also in Chinese. / Title from PDF title page (viewed on 07, October, 2016). / Chow, Chun Yin = Shuang ceng ji shan za ran liao ju he wu tai yang neng dian chi yan jiu / Zhou Junran. / Detailed summary in vernacular field only.

Wang, Mingdong. / Thesis (Ph.D.)--Chinese University of Hong Kong, 2011. / Includes bibliographical references. / Electronic reproduction. Hong Kong : Chinese University of Hong Kong, [2012] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Abstract also in Chinese.

A non-contact method characterizing the quantum efficiency of a solar cell using the microwave reflectance signature is presented in this thesis. Traditional solar cell quantum efficiency (QE) measurements are only possible near the completion of the fabrication process using contacts in direct physical connection with the metalized surface tabs to probe and extract charge carriers from the device. However, pressure within the solar metrology industry to report the spectral performance of the device earlier in the manufacturing process as part of the process control loop requires that a new non-contact method be developed. This thesis work contributes the development of a non-contact focused microwave reflectance technique capable of acquiring the full 365nm - 1100nm spectrum in under 1 minute. Unlike many similar Time Resolved Microwave Conductivity (TRMC) and Microwave Photoconductivity Decay (µPCD) systems based on the open-ended waveguide technique, this measurement is developed to perform measurements in the far-field. As such, a different mechanism for understanding the problem is presented using the modulated scatterer concept from antenna theory. Using a combination of high dielectric sensor pads and negative-index of refraction microwave lenses, we are able to tune the far-field field probe size from 5mm-150mm allowing for high speed single point in-line measurements or high spatial sensitivity laboratory measurements.

Pyrite (FeS2) has recently attracted significant interest as a photovoltaic material due to its promising optical properties, high photon to electron conversion yield, and low-cost raw materials. However, hopes have been tempered by recent discoveries that suggest the presence of hard to remove bulk sulfur defects. This research was focused on engineering and implementing the crystallization of pyrite from a sulfur rich solution to counteract the material's natural tendency to form bulk sulfur defects. Homoeptiaxial layers and single-crystal samples have been grown from tellurium sulfur melts with an Fe:S ratio of 1:4 using both natural and synthetic substrates. The homoepitaxial layer has been characterized using scanning electron microscopy (SEM), transmission electron microscopy (TEM), and high resolution transmission electron microscopy (HRTEM), confirming the epitaxial nature of the synthetic FeS2 layer, and X-ray and ultraviolet photoelectron spectroscopy (XPS and UPS) to better understand the energetics of the grown materials. Furthermore, epitaxial growth onto natural pyrite, in contrast to substrate etching, was established using sulfur-34 substitution and secondary ion mass spectrometry (SIMS). Growth onto synthetic pyrite was also described. Finally, the photovoltaic properties of homoepitaxial layers of high temperature solution growth pyrite onto a synthetic templating crystal was characterized using electrochemical methods.