Described herein are three projects centered on the synthesis of conducting polymer derivatives for various applications. The first is the novel synthesis of 9,9-dioctylfluorene-co-benzothiadiazole [F8BT] oligomers through solid phase synthesis for the study of the thermodynamics and kinetics of electron transfer in the polymer. The second endeavor involves the synthesis of a series of 4”,3’’’-dialkyl-2,2’:5’,2”:5”,2’’’:5’’’,2’’’’:5’’’’,2’’’’’-sexithiophenes for the studies on crystal packing and surface deposition of organic p-type semiconducting materials. Lastly is described the development of a conducting metallopolymer based on the ligand 2,6-Bis(4-(2,2’-bithiophen-5-yl)-1H-pyrazol-1-yl)pyridine for use in a drug delivery system. / text

[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.

Organic semiconductors (OSCs) present an electron mobility lower by several orders of magnitude than the hole mobility, giving rise to an electron-hole charge imbalance in organic devices such as organic light-emitting diodes (OLEDs) and organic light-emitting transistors (OLETs). In this thesis project, I tried to achieve an efficient electron transport and injection properties in opto-electronic devices, using inorganic n-type metal oxides (MOs) instead of organic n-type materials and a polyethyleneimine ethoxylated (PEIE) thin layer as electron transport (ETLs) and injection layers (EILs), respectively. In the first part of this thesis, inverted OLEDs were fabricated in order to study the effect of the PEIE layer in-between ZnO and two different emissive layers (EMLs): poly(9,9-dioctylfluorene-alt-benzothiadiazole) polymer (F8BT) and tris(8-hydroxyquinolinato) aluminum small molecule (Alq3), based on a solution and thermal evaporation processes, respectively. Different concentrations (0.80 %, 0.40 %) of PEIE layers were used to further study electron injection capability in OLEDs. After a series of optimizations in the fabrication process, the opto-electrical characterization showed high-performance of devices. The inverted OLEDs reported a maximum luminance over 104 cd m-2 and a maximum external quantum efficiency (EQE) around 1.11 %. The results were attributed to the additional PEIE layer which provided a good electron injection from MOs into EMLs. In the last part of the thesis, OLETs were fabricated and discussed by directly transferring the energy modification layer from OLEDs to OLETs. As metal oxide layer, ZnO:N was employed for OLETs since ZnO:N-based thin film transistors (TFTs) showed better performance than ZnO-based TFTs. Finally, due to their short life-time, OLETs were characterized electrically but not optically.