[pt] Este trabalho teve como objetivo comparar as diferentes influências que aditivos e tratamentos térmicos têm sobre as propriedades ópticas e elétricas de filmes finos semicondutores formados por polímeros contendo principalmente bitiofenos e fluorenos. Os polímeros contendo tiofenos em sequência, como o poli[(9,9-dioctilfluorenil-2,7-diil)co-bitiofeno] (F8T2), apresentam conformações cis e trans dependente da posição relativa dos átomos de enxofre, tendo suas propriedades alteradas de acordo com a proporção entre os domínios de ambas as conformações em um mesmo filme. Os átomos de iodo presentes no aditivo 1,8- diiodooctano são tidos como uma possível forma de alterar os agregados nesse polímero e, consequentemente, alterar as propriedades físicas do filme formado. Para aumentar o entendimento sobre os átomos diferentes de carbono e hidrogênio nos aditivos foram estudados os efeitos dos aditivos 1,8-diiodooctano, 1,8- octanoditiol e octano, que contém dois iodos, dois enxofres e não contém heteroátomos, respectivamente, em sua composição. Além disso, foi estudada a introdução do polímero PMMA (polimetilmetacrilato) de forma que alterasse a estrutura interna do filme fino e também foram estudados tratamentos térmicos em diferentes temperaturas, uma vez que parâmetros como tempo de evaporação do solvente também influenciam a formação e as propriedades do filme após seu crescimento. Outro ponto de interesse foi justamente a composição dos polímeros, para tal, foram estudados, além do F8T2, os polímeros poli(9,9-dioctilfloureno) (PFO), poli(9,9-dioctilfluoreno-cobenzotiadiazol) (F8BT) e poli(3-hexiltiofeno-2,5-diil) regiorregular (rrP3HT). Eles são formados, respectivamente, por bitiofenos e fluorenos, apenas fluorenos, fluorenos e benzotiadiazol e apenas politiofenos. Dessa forma, seria possível isolar as contribuições de cada grupo isolado e combinados com grupos que permitem ou não a mudança entre conformações. Os filmes foram depositados em substratos de vidro pela técnica de spin-coating e a caracterização foi feita com medidas de absorção, fotoluminescência e FTIR. Quando possível, foram realizadas medidas CELIV e corrente-tensão de dispositivos fotovoltaicos usando os polímeros como camada doadora de elétrons. Com este trabalho foi possível variar as intensidades dos picos de absorção e alterar o gap de energia dos polímeros. Destacando a ação do DIO, observou-se que a conformação cis do F8T2 é maximizada quando se utiliza 1 por cento do aditivo. Além disso, o DIO também aumenta a porcentagem de fase beta do PFO. Já para o P3HT, foi constatado um aumento no ordenamento do filme. / [en] This work aimed to compare the different influences that additives and heat treatments have on the properties of semiconductor thin films formed by polymers containing mainly bitiophenes and fluorenes. Polymers containing thiophenes in sequence, such as poly[(9,9-dioctylfluorene-2,7-diyl)co-bithiophene] (F8T2), have cis and trans conformations depending on the relative position of the sulfur atoms, having their optical and electrical properties altered according to the proportion between the domains of both conformations in the same film. The iodine atoms present in the additive 1,8-diiodooctane are considered as a possible way to change the aggregates in this polymer and, consequently, change the physical properties of the formed film. To increase the understanding of the atoms other than carbon and hydrogen in the additives, the effects of the additives 1,8-diiodooctane, 1,8- octanodithiol and octane, which contain two iodines, two sulfur and do not contain heteroatoms, respectively, were studied. In addition, the introduction of the PMMA (polymethylmethacrylate) polymer was studied in order to alter the internal structure of the thin film and, also, heat treatments at different temperatures were studied, since parameters such as solvent evaporation time and the available thermal energy also influence the formation and properties of the film after its growth. Another point of interest was precisely the composition of the polymers. For this purpose, in addition to F8T2, the polymers poly(9,9-dioctylflourene) (PFO), poly(9,9-dioctylfluorene-cobenzothiadiazole) (F8BT) and regioregular poly(3- hexylthiophene-2,5-diyl) (rrP3HT) were studied. They are formed, respectively, by bitiophenes and fluorenes, only fluorenes, fluorenes and benzothiadiazole and only polythiophenes. In this way, it would be possible to isolate the contributions of each isolated and combined groups that allow or not to change between conformations. The films were deposited on glass substrates using the spin-coating technique and the characterization was done via absorption, photoluminescence and FTIR measurements. When possible, CELIV and current-voltage measurements of photovoltaic devices were performed using the polymers as an electron donor layer. With this work it was possible to vary the intensities of the absorption peaks and to change the energy gap of the polymers. Highlighting the action of DIO, it was observed that the cis conformation of F8T2 is maximized when 1 percent of the additive is used. In addition, DIO also increases the percentage of beta phase of PFO. For P3HT, on the other hand, there was an increase in the ordering of the film.

This thesis explores the commercial links between Scotland and France in the long seventeenth century, with a focus on the Scottish mercantile presence in France’s Atlantic ports, particularly during periods of domestic and international upheaval. This study questions long-held assumptions regarding this relationship, asserting that the ‘Auld Alliance’ continued throughout the period, despite the widely held belief that it ended in 1560. Such assumptions have led scholars largely to ignore the continuing commercial relationship between Scotland and France in the long seventeenth century, focusing instead on the ‘golden age’ of the Auld Alliance or the British relationship with France in the eighteenth century. Such assumptions have been fostered by the methodological approaches used in the study of economic history to date. While I acknowledge the relevance of traditional quantitative approaches to economic history, such as those pioneered by T. C. Smout and which continue to be followed by historians such as Philipp Rössner, I follow alternative methods that have been recently employed by scholars such as Henriette de Bruyn Kops, Sheryllynne Haggerty, Xavier Lamikiz, Allan Macinnes and Steve Murdoch. These scholars have pioneered methodologies that prioritise private sources, allowing us to delve into the motivations and actions of the individuals who actually effected trade, be they merchants, factors, skippers or manufacturers. The core of my research has therefore entailed the discovery and use of previously untapped archival material including account books, letter books and correspondence, which illuminate the participation of these individuals in international trade. Such a study, while filling a specific gap in our understanding of Scotland’s overseas relations, applies a more social methodology to this topic, suggesting that scholars’ approaches need to be fundamentally altered if we are truly to understand the whole picture of Scotland’s, or indeed any nation’s, commercial relationships or wider economic position.