A crescente demanda energética mundial vem estimulando pesquisas em novas fontes de energia limpa e renovável e de baixo custo. Nesse contexto, as células solares orgânicas (fotovoltaicos orgânicos – OPVs) destacam-se como uma alternativa promissora no campo dos fotovoltaicos. Por serem fabricadas a partir de soluções eletrônicas, sua fabricação se dá deposição sobre substratos rígidos ou flexíveis, e com isso, também por técnicas de impressão. Muitas moléculas poliméricas têm mostrados excelentes resultados, porém o desempenho das células dependem também da morfologia do filme ultrafino da camada ativa, a qual depende do processamento e sobretudo da atividade dos solventes orgânicos. Até o momento, a maioria dos solventes usados para a fabricação das OPVs de alto desempenho é da classe dos halogenados, como por exemplo, o clorobenzeno e o 1,2-diclorobenzeno. Esses solventes, além de exibirem alto custo de produção, apresentam toxicidade relativamente alta, com impactos adversos à saúde humana e ao meio ambiente. Visto que a tecnologia dos OPVs está próxima de sua comercialização, a procura por solventes alternativos de baixa toxicidade coloca-se como um desafio a essa área. Neste trabalho, identificou-se por meio dos parâmetros de solubilidade de Hansen, um solvente da classe dos não halogenados e não aromáticos com baixa toxicidade ao ser humano e ambientalmente amigável para ser aplicado como solvente de processamento de células solares orgânicas do tipo heterojunção de volume (BHJ). Para isso, os possíveis solventes foram avaliados segundo os parâmetros de solubilidade de Hansen para os polímeros, P3HT e PTB7-Th, e para as moléculas PC61BM e PC71BM, levando em consideração os critérios de riscos com base na ficha de segurança de produtos químicos. Desse modo, a ciclohexanona foi selecionada por conter as características desejadas para o estudo proposto no presente trabalho. As soluções de P3HT e de PTB7- Th em ciclohexanona foram avaliadas quanto à influência da temperatura das soluções na conformação dos polímeros, a partir da técnica de termocromismo. Os resultados revelam necessidade de aquecimento para que haja uma conformação menos agregada tanto do P3HT quanto do PTB7-Th em solução de ciclohexanona. Os filmes de P3HT:PC61BM e PTB7-Th:PC71BM foram depositados pela técnica de spin-coating sobre substratos de vidro e estudos sobre sua morfologia foram realizados por técnicas de imagens de microscopia óptica, AFM e medidas de absorção pela técnica UV-vis, e correlacionadas ao desempenho das células fabricadas. Os resultados obtidos foram promissores uma vez que nesse trabalho conseguimos células de até 5,5 % de eficiência. / The growing global demand for energy has been stimulating research into new sources of clean and renewable energy and low cost. In this context, organic solar cells (organic photovoltaic - OPVs) stand out as a promising alternative in the field of photovoltaics. Because they are manufactured from electronic solutions, it can be deposited on rigid or flexible substrates, facilitating their production by printing techniques. Many polymer molecules have shown excellent results, but the performance of the cells also depends on the morphology of the ultrathin film of the active layer, which depends on the processing and above all the activity of the organic solvents. To date, most of the solvents used in the manufacture of high-performance OPVs belong to the halogen class, for example chlorobenzene and 1,2-dichlorobenzene. These solvents, in addition to exhibiting high cost of production, have relatively high toxicity, with adverse impacts on human health and the environment. Since the technology of OPVs is close to commercialization, the search for low-toxicity alternative solvents poses a challenge in this area. In this work, Hansen\'s solubility parameters were used to identify solvents of non-halogenated and non-aromatic class with low toxicity to humans and environmentally friendly, as substitutes of traditional solvents used to process organic solar cells (BHJ). For this, several solvents were evaluated according to the Hansen solubility parameters for the polymers, P3HT and PTB7-Th, and for the molecules PC61BM and PC71BM, taking into account the risk criteria based on the chemical safety data sheet. The solutions of P3HT and PTB7-Th in cyclohexanone were evaluated taking into account the influence of the temperature of the solutions on the conformation of the polymers, using the thermochromic technique. The solutions of P3HT and PTB7-Th in cyclohexanone were evaluated taking into account the influence of the temperature of the solutions on the conformation of the polymers, using the thermochromic technique. The resulted morphology was then correlated with the devices performance. The results obtained were promising since in this work we obtained cells of up to 5.5% efficiency.

Submitted by MAIZA DA SILVA OZÓRIO null (ozoriounesp@gmail.com) on 2018-02-26T15:23:33Z No. of bitstreams: 1 dissertação_maiza_versão_final_corrigida.pdf: 3955466 bytes, checksum: 08f98a38963076999f04ee08c2e89954 (MD5) / Approved for entry into archive by Claudia Adriana Spindola null (claudia@fct.unesp.br) on 2018-02-26T16:14:51Z (GMT) No. of bitstreams: 1 ozorio_ms_me_prud.pdf: 3955466 bytes, checksum: 08f98a38963076999f04ee08c2e89954 (MD5) / Made available in DSpace on 2018-02-26T16:14:51Z (GMT). No. of bitstreams: 1 ozorio_ms_me_prud.pdf: 3955466 bytes, checksum: 08f98a38963076999f04ee08c2e89954 (MD5) Previous issue date: 2016-06-28 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Um dos atuais desafios da eletrônica orgânica é a obtenção de semicondutores com alta mobilidade que forme filmes com boa morfologia quando depositado/impresso por solução, resultando em boa uniformidade e reprodutibilidade dos dispositivos. O poli(3- hexiltiofeno) (P3HT) e o 6,13-(triisopropilsililetinil)pentaceno (TP) estão entre os semicondutores orgânicos mais utilizados. O TP tem como característica a formação de estruturas cristalinas, e desse modo, apresenta mobilidade muito maior que o P3HT, no entanto é difícil de obter filmes com boa morfologia e resultados reprodutíveis. Visando um material semicondutor que apresente mobilidade significativamente melhor que a do P3HT e uma morfologia melhor que a do TP, estudou-se compósitos a partir da mistura destes materiais (P3HT:TP) para aplicação em transistores orgânicos de efeito de campo (OFETs), utilizando óxido de alumínio anodizado (Al2O3) tratado com HMDS como dielétrico de gate. Para análise da morfologia dos compósitos semicondutores de P3HT:TP usou-se microscopia eletrônica de varredura (MEV), microscopia de força atômica (AFM) e microscopia óptica (MO). Análise óptica foi feita através de medidas de fotoluminescência (PL) e de tempo de decaimento por fotoluminescência. Espectroscopia Raman e FTIR foram utilizadas para análises estruturais. No modo transistor a caracterização foi feita através de curvas de saída e transferência. Através das caracterizações elétricas determinou-se os parâmetros do semicondutor, tais como, mobilidade, voltagem limiar de chaveamento e razão entre o estado ligado e desligado. A morfologia da blenda semicondutora apresentou características específicas de cada material, ressaltando a formação de aglomerados. Observou-se diferenças bastantes consideráveis na morfologia do compósito em função da variação do solvente e da cinética de deposição dos filmes. Imagens de MEV mostram regiões cristalinas do TP dispersas na matriz polimérica do P3HT, onde o tamanho, forma e distribuição dos cristalitos dependem do tratamento dado à superfície do isolante. O aumento da concentração de TP dificulta a formação de compósitos com boas características. A melhor mobilidade foi obtida com o compósito 50P3HT:50TP, apresentando valores na ordem de 10- 3 cm2V -1 s -1 . / One of the current challenges of organic electronics is the development of semiconductors with high mobility to form films with good morphology when deposited/printed by solution, resulting in good uniformity and reproducibility of the devices. The poly (3-hexylthiophene) (P3HT) and 6,13-(triisopropilsililetinil)pentacene (TP) are among the most widely used organic semiconductors. The TP films are constituted by crystalline lamellar structures, and thus has greater mobility than the P3HT, however, it is difficult handling it to obtain films with good morphology and reproducible results. Targeting a semiconductor material with significantly better mobility than that of P3HT and better morphology than that of TP, we studied composites of these materials (P3HT: TP) for using in organic field effect transistors (OFETs). The transistor was prepared depositing the solution of the semiconductor composite, by spin coating, on the aluminium oxide, obtained by anodization and treated with HMDS, followed by the thermal evaporation of gold on the top, to form the drain and source electrodes. For analysis of the morphology of the composites semiconductors (P3HT: TP) was used scanning electron microscopy (SEM), atomic force microscopy (AFM) and optical microscopy (OM). Optical analysis was performed using photoluminescence (PL) measurements and decay time by photoluminescence. FTIR and Raman spectroscopy were used to structural analysis. In mode transistor, characterization was performed using output and transfer curves. Through the electrical characterizations determined the semiconductor parameters such as mobility, threshold-switching voltage and the ratio between the current in “on” and “off” states. The morphology of the semiconductor composite presented specific characteristics of each material, emphasizing the formation of agglomerates. It has been observed quite considerable differences in the morphology of the composite depending on the solvent and the variation of the film deposition kinetics. SEM images show crystalline regions TP dispersed in the polymeric matrix of P3HT, where the shape, size and distribution of crystallites depend on the treatment of the surface of the dielectric. The increase in TP concentration hinders the formation of composites with good characteristics. The best mobility was obtained with the composite 50P3HT: 50TP, with values in the order of 10- 3 cm2V -1 s -1 .

Abstract Organic semiconductors (OSCs) and graphene are two classes of conjugated materials that hold promise to create flexible electronic displays, high speed transistors, and low-cost solar cells. Crucial to understanding the behavior of these materials is understanding the effects metallic contacts have on the local charge environment. Additionally, characterizing the charge carrier transport behavior within these materials sheds light on the physical mechanisms behind transport. The first part of this thesis examines the origin of the low-temperature, high electric field transport behavior of OSCs. Two chemically distinct OSCs are used, poly-3(hexylthiophene) (P3HT) and 6,13- bis(triisopropyl-silylethynyl) (TIPS) pentacene. Several models explaining the low-temperature behavior are presented, with one using the Tomonaga-Luttinger liquid (TLL) insulator-to-metal transition model and one using a field-emission hopping model. While the TLL model is only valid for 1-dimensional systems, it is shown to work for both P3HT (1D) and TIPS-pentacene (2D), suggesting the TLL model is not an appropriate description of these systems. Instead, a cross-over from thermally-activated hopping to field-emission hopping is shown to explain the data well. The second part of this thesis focuses on the interaction between gold and platinum contacts and graphene using suspended graphene over sub-100 nanometer channels. Contacts to graphene can strongly dominate charge transport and mobility as well as significantly modify the charge environment local to the contacts. Platinum electrodes are discovered to be strong dopants to graphene at short length scales while gold electrodes do not have the same effect. By increasing the separation distance between the electrodes, this discrepancy is shown to disappear, suggesting an upper limit on charge diffusion from the contacts. Finally, this thesis will discuss a novel technique to observe the high-frequency behavior in OSCs using two microwave sources and an organic transistor as a mixer. A theoretical model motivating this technique is presented which suggests the possibility of retrieving gigahertz charge transport phenomena at kilohertz detection frequencies. The current state of the project is presented and discrepancies between devices made with gold and platinum electrodes measured in the GHz regime are discussed.

The electronic structures at the hetero interface of Poly(3-hexylthiophene): methanofullerene (P3HT:PCBM) have a great improvement on the solar cell efficiency due to the formation of bicontinuous nanoscaled phase separation which will enhance charge separation and carrier transport. In the present work, cross-sectional scanning tunneling microscopy and scanning tunneling spectroscopy measurements are utilized to obtain the in-situ atomic-scale band structure across the interface between P3HT and PCBM directly. The distribution of PCBM volume concentration of organic films was also analyzed and discussed in the work.

Polymers are with low carrier mobility. If polymer solar cells are to exhibit high power conversion efficiencies, their carrier mobilities must be improved. Metallic NPs are promising materials for use in polymer solar cells because of their high conductivities. In this work, we studied the carrier transport characteristic of metallic nanoparticle blending into polymers. We blended Pt nanoparticles (Pt NPs) and Pd nanoparticles (Pd NPs) into polymers to improve carrier mobility, and enhance the power conversion efficiency of the polymer solar cell. P3HT was used as a donor material because of its high stability and with high absorption in visible light. PCBM was used as a acceptor material because of its high stability and with high electron transportation. We blended modified Pt NPs and Pd NPs into the P3HT:PCBM active layer, with the device configurations of ITO/PEDOT:PSS/P3HT:PCBM: Pt NPs/Al and ITO/PEDOT:PSS/P3HT:PCBM:Pd NPs/Al, respectively polymer solar cells measured was under AM 1.5G 100mW/cm2 illumination. When we blended Pt NPs into the active layer, the open-circuit remained 0.64V, the short-circuit current increased from 6.67mA/cm2 to 9mA/cm2, the power conversion efficiency increased from 1.96% to 3.08%. When we blended Pd NPs into the active layer, the open-circuit remained 0.62V, the short-circuit current increased from 6.33mA/cm2 to 7.33mA/cm2, the power conversion efficiency increased from 1.7% to 2.48%. The enhanced efficiency originated from the increased carrier mobility of the active layer when the Pt NPs or Pd NPs were present.

Insight into the relationship between the Ionization Energy (IE) offsets between donor and acceptor materials and the performance of the organic solar cells (OSC) could improve the charge generation efficiency. Charge generation can proceed through two different paths in Bulk Heterojunction (BHJ) based OSCs which are electron transfer from donor to acceptor and hole transfer from acceptor to donor. Electron transfer can be controlled by electron affinities and hole transfer can be controlled by ionization energies. In this work, large IE offsets were investigated in poly(3-hexylthiophene-2,5-diyl)(P3HT):Non Fullerene Acceptor (NFA) based OSCs by fabricating and characterizing devices, also conducting several experiments to optimize the processing conditions for the devices. These results provide an overview of the charge transfer and IE offsets dependence, also a general picture of the photophysics in P3HT:NFAs based OSCs. Moreover, using wide bandgap polymer donor which has shallow IE such as P3HT with low-bandgap NFAs may provide sufficient IE offsets between donor and acceptors enabled us to reach the inverted Marcus regime. In this regime, the electron transfer rate decreases upon decreasing the charge transfer (CT) state energy compared to the exciton energy. The decrease of the internal quantum efficiency (IQE) upon increasing the IE offset suggests that we are in that regime.

This thesis focuses on the physics of nanoplasmonic systems for dispersive and lossy media. Gold nanoparticles in P3HT (poly(3-hexylthiophene)) and PMMA (poly(methyl methacrylate)) are analyzed both theoretically and experimentally. It is found in both cases that the presence of P3HT narrows the linewidth of the gold plasmon peak. This is a counter-intuitive result, and this narrowing of the linewidth by a lossy material is analyzed in detail. It is found that dispersion in both the real and imaginary parts of the permittivity of the surrounding medium can significantly affect the linewidth. Another plasmonic phenomena was also researched. An atomic energy level model of erbium was constructed and used to solve a rate equation to calculate the far-field emission enhancement from an erbium atom nearby a gold nanorod when the dark mode is excited. Normally a small emission enhancement is expected in the far field since dark modes do not couple strongly to radiation, but in experiments this dark field emission enhancement was seen to be significant. The results of the calculation were compared to this previous experimental result. Although the incident power dependence of the calculated 980 nm emission line agreed with experiments, the 650 nm emission line power dependence and the calculated emission enhancement did not, and so more work needs to be done with this model to explain the experimental results. / Graduate

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Based on the solar cell¡¦s four characteristic parameter open-circuit voltage (Voc) makes the discussion.The study of the relation VOC¡¦s paper uses empirical formula. VOC¡¦s formula is ¡§VOC=(1/e)(¡UEDonorHOMO¡W-¡UEAcceptorLUMO¡W)-0.3V¡¨. We can know that VOC related to donor material¡¦s HOMO and acceptor material¡¦s LUMO, if we need a high VOC, it can change the structure of donor material to have higher HOMO value, as well as the acceptor material have lower LUMO value. Our active layer except poly(3-hexylthiophene) (P3HT) and [6,6]-phenyl-C61-Butyric acid methyl ester (PCBM), the third material was blended to discuss their effect on the VOC. Two kind of different bromined-P3HT (Br-P3HT) were used 40% and 100% bromined-P3HT to blend in active layer. Their Three materials blended under the different weight percent and the basic device configurations in this study was ITO / PEDOT : PSS / P3HT : Br-P3HT : PCBM / Al , efficiency was measured under AM 1.5G 100mW/cm2 illumination. When blended Br-P3HT(100%) in the active layer, VOC increased from 0.6V to 0.68V and the surface roughness makes short-circuit current and fill factor, increased make lower power conversion efficiency. When blended Br-P3HT(40%) into the active layer, not only can increase VOC to 0.66V, but influence the short-circuit current and the fill factor. The power conversion efficiency changed from 2.20% to 2.46%.