elementares da eletrônica orgânica, vêm sendo desenvolvidos e integrados para realização de dispositivos eletrônicos de baixo custo, alto volume e flexíveis. Nesta tese foi proposta uma tecnologia para a construção de OFETs sobre substrato flexível e a caracterização destes dispositivos foi feita. Transistores com diferentes comprimentos de canal (L= 5, 10, 20 e 40 μm) foram construídos e avaliados. As características e configuração do poli (álcool vinílico) (PVA) como dielétrico de porta foram definidas através da otimização da reticulação, grau de hidrólise e peso molecular. O PVA utilizado como dielétrico de porta foi de alto peso molecular, hidrolização incompleta e reticulado com dicromato de amônia. O desafio de compatibilização entre os filmes de PVA e poli (3-hexiltiofeno) (P3HT) com diferentes polaridades foi superado e abriu caminho para construção de OFETs e capacitores, estes últimos usados para extrair a capacitância por unidade de área do conjunto PVA-P3HT. Os processos desenvolvidos de fotolitografia e de oxidação por plasma de oxigênio possibilitaram a construção de transistores flexíveis inéditos de Ni-P3HT-PVA-Al com uma arquitetura top-gate, bottom-contacts. Os transistores apresentaram boas características de saída, baixa tensão de operação (< |-6 V|), boa mobilidade (0,015 cm2/V*s) e razões ION/IOFF aceitáveis (~300). A resistência de contato e mobilidade efetiva foram obtidas através do método de linhas de transmissão. Uma boa estabilidade temporal foi atingida, porém ocorreram instabilidades na operação quando os transistores foram testados. A corrente do transistor não se manteve estável, primeiramente aumentou e depois diminuiu com a realização de sucessivas medidas. As razões deste comportamento foram discutidas. Inversores foram demonstrados e caracterizados. O aperfeiçoamento da tecnologia desenvolvida possibilitará a construção de circuitos orgânicos analógicos e digitais para aplicações cotidianas que demandem baixo custo e alto volume. / Organic field effect transistors (OFETs), the elementary components of organic electronics, are constantly developed and integrated to realize low cost, high volume, flexible electronic devices. In this thesis a technology for creating OFETs on flexible substrates is proposed and their characterization is performed. Flexible transistors with different channel lengths (L= 5, 10, 20 and 40 μm) were built and evaluated. The characteristics and configurations of the poly (vinyl alcohol) (PVA) as gate dielectric were defined through the optimization of crosslinking, the degree of hydrolysis and the molecular weight. The chosen PVA is cross-linked with ammonium dichromate, has a high molecular weight and incomplete hydrolization. The challenge of integrating polymers of different polarities: PVA and poly (3-hexyl thiophene) (P3HT), the chosen organic semiconductor, was overcome and opened a path to the construction of OFETs and capacitors. From the later capacitance per unit area was extracted. The developed processes of photolithography and oxygen plasma etching allowed the construction of unprecedented Ni-P3HT-PVA-Al flexible top-gate, bottomcontacts transistors. The transistors showed good output characteristics, low operation voltages (< |-6 V|), acceptable carrier mobilities (0,015 cm2/V*s) and ION/IOFF fractions (~300). Contact resistance and effective mobility were extracted through transmission line method. The transistors showed great temporal stability, but when operated instabilities occurred. The transistor output current first increased and later degraded with successive testing. Organic PMIS inverters were demonstrated and characterized. The optimization of this technology may lead to construction of flexible logic organic devices for everyday applications.

elementares da eletrônica orgânica, vêm sendo desenvolvidos e integrados para realização de dispositivos eletrônicos de baixo custo, alto volume e flexíveis. Nesta tese foi proposta uma tecnologia para a construção de OFETs sobre substrato flexível e a caracterização destes dispositivos foi feita. Transistores com diferentes comprimentos de canal (L= 5, 10, 20 e 40 μm) foram construídos e avaliados. As características e configuração do poli (álcool vinílico) (PVA) como dielétrico de porta foram definidas através da otimização da reticulação, grau de hidrólise e peso molecular. O PVA utilizado como dielétrico de porta foi de alto peso molecular, hidrolização incompleta e reticulado com dicromato de amônia. O desafio de compatibilização entre os filmes de PVA e poli (3-hexiltiofeno) (P3HT) com diferentes polaridades foi superado e abriu caminho para construção de OFETs e capacitores, estes últimos usados para extrair a capacitância por unidade de área do conjunto PVA-P3HT. Os processos desenvolvidos de fotolitografia e de oxidação por plasma de oxigênio possibilitaram a construção de transistores flexíveis inéditos de Ni-P3HT-PVA-Al com uma arquitetura top-gate, bottom-contacts. Os transistores apresentaram boas características de saída, baixa tensão de operação (< |-6 V|), boa mobilidade (0,015 cm2/V*s) e razões ION/IOFF aceitáveis (~300). A resistência de contato e mobilidade efetiva foram obtidas através do método de linhas de transmissão. Uma boa estabilidade temporal foi atingida, porém ocorreram instabilidades na operação quando os transistores foram testados. A corrente do transistor não se manteve estável, primeiramente aumentou e depois diminuiu com a realização de sucessivas medidas. As razões deste comportamento foram discutidas. Inversores foram demonstrados e caracterizados. O aperfeiçoamento da tecnologia desenvolvida possibilitará a construção de circuitos orgânicos analógicos e digitais para aplicações cotidianas que demandem baixo custo e alto volume. / Organic field effect transistors (OFETs), the elementary components of organic electronics, are constantly developed and integrated to realize low cost, high volume, flexible electronic devices. In this thesis a technology for creating OFETs on flexible substrates is proposed and their characterization is performed. Flexible transistors with different channel lengths (L= 5, 10, 20 and 40 μm) were built and evaluated. The characteristics and configurations of the poly (vinyl alcohol) (PVA) as gate dielectric were defined through the optimization of crosslinking, the degree of hydrolysis and the molecular weight. The chosen PVA is cross-linked with ammonium dichromate, has a high molecular weight and incomplete hydrolization. The challenge of integrating polymers of different polarities: PVA and poly (3-hexyl thiophene) (P3HT), the chosen organic semiconductor, was overcome and opened a path to the construction of OFETs and capacitors. From the later capacitance per unit area was extracted. The developed processes of photolithography and oxygen plasma etching allowed the construction of unprecedented Ni-P3HT-PVA-Al flexible top-gate, bottomcontacts transistors. The transistors showed good output characteristics, low operation voltages (< |-6 V|), acceptable carrier mobilities (0,015 cm2/V*s) and ION/IOFF fractions (~300). Contact resistance and effective mobility were extracted through transmission line method. The transistors showed great temporal stability, but when operated instabilities occurred. The transistor output current first increased and later degraded with successive testing. Organic PMIS inverters were demonstrated and characterized. The optimization of this technology may lead to construction of flexible logic organic devices for everyday applications.

abstract: In this work a newly fabricated organic solar cell based on a composite of fullerene derivative [6,6]-phenyl-C61 butyric acid methyl ester (PCBM) and regioregular poly (3-hexylthiophene) (P3HT) with an added interfacial layer of AgOx in between the PEDOT:PSS layer and the ITO layer is investigated. Previous equivalent circuit models are discussed and an equivalent circuit model is proposed for the fabricated device. Incorporation of the AgOx interfacial layer shows an increase in fill factor (by 33%) and power conversion efficiency (by 28%). Moreover proper correlation has been achieved between the experimental and simulated I-V plots. The simulation shows that device characteristics can be explained with accuracy by the proposed model. / Dissertation/Thesis / Masters Thesis Electrical Engineering 2015

The importance of renewable energy sources is becoming clearer and clearer as unsustainable energy sources are running out and global warming is getting worse. Energy derived from sunlight is already commonly used, but more energy can be produced from sunlight when solar cells become cheaper. Organic solar cells use organic compounds as semiconductors which can be prepared from solutions, resulting in lower production costs. However, these semiconductors;Poly(3-hexylthiophene) and [6,6]-Phenyl-C61-butric acid methyl ester, are commonly dissolved inhalogenated and aromatic solvents. These solvents have toxic properties, which is why alternative solvents should be identified. Potential solvents were predicted by using the Hansen solubilityparameters and thin films were prepared by spin-coating the solutions. The thin films were evaluated with absorption spectroscopy, the fluorescence spectroscopy and atomic force microscopy. Since the alternative solvents had lower solubilites than the commonly used solvents, i.e., chlorobenzene, ortho-dichlorobenzene and chloroform, the absorption of the films with new solvents were lower as well. Using tetrahydrofuran resulted in the highest absorption of the used solvents, while xylene hada better film morphology. Increasing the absorption was attempted by spin-coating multiple thin films on top each other or by using a lower rotational speed. Spin-coating multiple films had nouniform effect on the absorption, while lowering the rotational speed increased the absorption, but not enough to equal the original absorption. Contrasting the results of the absorption spectra, the morphology improved when multiple layers were used while the film with the lower rotational speed’s morphology got worse. In conclusion, tetrahydrofuran and xylene are the best alternative solvents and using multiple layers as well as decreasing the rotational speed show improvements oneither the morphology or the absorption.

A novel UHV microcalorimeter has been used to study the interaction between calcium and three polymers: MEH-PPV, MEH-PPP and P3HT. All three polymers behave differently in their reaction kinetics with calcium. On MEH-PPV we measure 45 μJ/cm² of heat generated in excess of the heat of bulk metal growth, 120 μJ/cm² for MEH-PPP, and 100 μJ/cm² for P3HT. Comparison of the MEH-PPV and MEHPPP data indicate that the initial reaction of calcium with MEH-PPV occurs at the vinylene group. We propose, based on hypothetical models, that calcium reacts with the vinylene groups of MEH-PPV with a reaction heat of 360 kJ/mol and at a projected surface density of 1.7 sites/nm², while it reacts with the phenylene groups of MEH-PPP in a two-step process with reaction heats of 200 and 360 kJ/mol respectively, at a projected surface density of 3.5 sites/nm². Optical absorption experiments, using either a 1.85 eV diode laser or a xenon lamp coupled to a scanning monochromator, have also been performed using the same calorimeter sensor. In the case of MEH-PPV, using the laser we find an optical absorption cross-section of 3E-¹⁷ cm² per incident calcium atom at low coverages. The change in absorptance at higher coverages correlates perfectly with the population of reacted Ca atoms determined calorimetrically. The size of the absorbance cross-section, and its position just within the band gap of the polymer, are consistent with the reaction being one of polaron formation. Calcium does not appear to dope P3HT, while the photon energy range of 1.5 to 3.75 eV used in these experiments is likely too small for probing polaronic energy states in MEH-PPP. / Science, Faculty of / Chemistry, Department of / Graduate

No description available.

Research in recent years on novel materials in organic solar cells (OSCs) have contributed to a rapid advancement in OSC efficiency. Here, OSCs with the well-studied organic semiconductors poly(3-hexylthiophene):[6,6]-phenyl C60-butyric acid methylester (P3HT:PCBM) in a bulk heterojunction structure were prepared to establish a baseline procedure for fabrication and spin-sensitive spectroscopy. Spin-sensitive spectroscopy can be used to probe the spin-dependent processes and loss mechanism in OSCs. Understanding the microscopic processes enables research targeting loss mechanisms directly, which opens up for higher efficiency OSCs. Measurements with continuous wave electrically detected magnetic resonance (cwEDMR), continuous wave electron paramagnetic resonance (cwEPR) and transient (tr)EDMR were set up and followed by an initial study on the spin-dependent processes and their influence on the photocurrent. Signals from spin-dependent processes in the samples were seen for the three experiment series carried out, and well-functioning OSCs with consistent results were prepared. This thesis and the presented baseline fabrication and experimental setup procedures provide with valuable learnings for future research in the group AG Behrends enabling fabrication and spin-sensitive studies on novel materials in OSCs. It was found that post-processing annealing at 120 C for 5 min reduces S-shape behaviour in current-voltage curves, and over all improves poor current-voltage characteristics of the OSC samples fabricated. Further, influence from PEDOT:PSS was seen in cwEPR spectroscopy, indicating the presence of traps or free radicals in the PEDOT:PSS. In cwEDMR spectroscopy of the OSCs it was shown that the spin processes of bias-induced and photo-induced charge carriers influence the photocurrent in the same way. Finally, the authors suggest that results from spin-sensitive spectroscopy of degraded OSCs cannot be applied to non-degraded OSCs.

All-polymer solar cells (APSC) are a class of organic solar cells in which hole and electron transporting phases are made of conjugated polymers. Unlike polymer/fullerene solar cell, photoactive material of APSC can be designed to have hole and electron transporting polymers with complementary absorption range and proper frontier energy level offset. However, the highest reported PCE of APSC is 5 times less than that of polymer/fullerene solar cell. The low PCE of APSC is mainly due to: i) low charge separation efficiency; and ii) lack of optimal morphology to facilitate charge transfer and transport; and iii) lack of control over the exciton and charge transport in each phase. My research work is focused towards addressing these issues. The charge separation efficiency of APSC can be enhanced by designing novel electron transporting polymers with: i) broad absorption range; ii) high electron mobility; and iii) high dielectric constant. In addition to with the above parameters chemical and electronic structure of the repeating unit of conjugated polymer also plays a role in charge separation efficiency. So far only three classes of electron transporting polymers, CN substituted PPV, 2,1,3-benzothiadiazole derived polymers and rylene diimide derived polymers, are used in APSC. Thus to enhance the charge separation efficiency new classes of electron transporting polymers with the above characteristics need to be synthesized. I have developed a new straightforward synthetic strategy to rapidly generate new classes of electron transporting polymers with different chemical and electronic structure, broad absorption range, and high electron mobility from readily available electron deficient monomers. In APSCs due to low entropy of mixing, polymers tend to micro-phase segregate rather than forming the more useful nano-phase segregation. Optimizing the polymer blend morphology to obtain nano-phase segregation is specific to the system under study, time consuming, and not trivial. Thus to avoid micro-phase segregation, nanoparticles of hole and electron transporters are synthesized and blended. But the PCE of nanoparticle blends are far less than those of polymer blends. This is mainly due to the: i) lack of optimal assembly of nanoparticles to facilitate charge transfer and transport processes; and ii) lack of control over the exciton and charge transport properties within the nanoparticles. Polymer packing within the nanoparticle controls the optoelectronic and charge transport properties of the nanoparticle. In this work I have shown that the solvent used to synthesize nanoparticles plays a crucial role in determining the assembly of polymer chains inside the nanoparticle there by affecting its exciton and charge transport processes. To obtain the optimal morphology for better charge transfer and transport, we have also synthesized nanoparticles of different radius with surfactants of opposite charge. We propose that depending on the radius and/or Coulombic interactions these nanoparticles can be assembled into mineral structure-types that are useful for photovoltaic devices.

No description available.

No description available.