The creation of organic electronics is not only an attractive replacement for amorphous silicon devices, but offers the ability to produce novel technologies such as flexible displays and chemical or biological sensors. Control of the semiconducting film for such devices is of great importance. The fabrication of monolayer devices of a high performance offer a desirable way of creating high sensitivity sensors. Achieving a high level of performance for ultra-thin and monolayer devices, where the charge transport layer is effectively the thickness of the film, requires the careful control of deposition conditions. Thin films of the molecule 5,5'-bis(4-n-hexylphenyl)-2,2'-bithiophene (PTTP) were investigated with respect to their crystal structure, growth dynamics and device performance. Optimised conditions led to the highest reported performance for PTTP, to the best of our knowledge, with mobilities greater than 0.1 cm2V-1s-1. These results allowed the creation of monolayer and multilayer devices, resulting in a saturation thickness of approximately 2.1 monolayers, where the bulk performance was reached. This confirmed the presence of the conduction channel within the first few monolayers and could potentially lead to an optimised device for chemical or biological sensing. The development of a solution processed method for creating monlayers of PTTP was also investigated. Creating a compound with the ability to self assemble on a surface, allowing a controlled monolayer to form, involved the use of a trichlorosilane anchoring group attached to a PTTP core by an alkyl spacer. Solution processed self assembled monolayer field effect transistors (SAMFETs) were formed in less than 10 hours, reaching mobilities as high as 1.7 X 10-2 cm2V-1s-1 . This simple method for creating transistors could further the use of monolayer devices in sensing applications and integrated circuits. Furthermore, the development of solution processed PTTP was undertaken. By blending the small molecule with the insulating polymer PMMA, phase separation of the components led to the creation of thin, crystalline films of PTTP. Working devices were fabricated that required as little as 0.05 \% w/v of the small molecule. This attractive method, of reducing the required material and combination of both insulating and semiconducting components, is a versatile approach to greatly simplify the device processing steps required.

There has been a remarkable progress in the development of organic electronic materials since the discovery of conducting polymers more than three decades ago. Many of these materials can be processed from solution, in the form as inks. This allows for using traditional high-volume printing techniques for manufacturing of organic electronic devices on various flexible surfaces at low cost. Many of the envisioned applications will use printed batteries, organic solar cells or electromagnetic coupling for powering. This requires that the included devices are power efficient and can operate at low voltages. This thesis is focused on organic thin-film transistors that employ electrolytes as gate insulators. The high capacitance of the electrolyte layers allows the transistors to operate at very low voltages, at only 1 V. Polyanion-gated p-channel transistors and polycation-gated n-channel transistors are demonstrated. The mobile ions in the respective polyelectrolyte are attracted towards the gate electrode during transistor operation, while the polymer ions create a stable interface with the charged semiconductor channel. This suppresses electrochemical doping of the semiconductor bulk, which enables the transistors to fully operate in the field-effect mode. As a result, the transistors display relatively fast switching (≤ 100 µs). Interestingly, the switching speed of the transistors saturates as the channel length is reduced. This deviation from the downscaling rule is explained by that the ionic relaxation in the electrolyte limits the channel formation rather than the electronic transport in the semiconductor. Moreover, both unipolar and complementary integrated circuits based on polyelectrolyte-gated transistors are demonstrated. The complementary circuits operate at supply voltages down to 0.2 V, have a static power consumption of less than 2.5 nW per gate and display signal propagation delays down to 0.26 ms per stage. Hence, polyelectrolyte-gated circuits hold great promise for printed electronics applications driven by low-voltage and low-capacity power sources.

[pt] O Alq3 é um dos mais importantes semicondutores orgânicos utilizados como transportador de elétrons e emissor em dispositivos eletroluminescentes (OLEDs). Este trabalho apresenta o estudo das propriedades ópticas, eletroquímicas, elétricas e morfológicas de três complexos baseados em íons de terras raras (TR) ligados à 8-hidroxiquinolina (q), Li[TR(q)4] (TR igual a La3mais, Y3mais e Lu3mais). Os espectros de absorção na região UV-Vis possuem máximos em 382nm para os complexos de Y3mais/La3mais e em 388nm para o complexo de Lu3mais. Os espectros de fotoluminescência dos complexos correspondem à emissão da (q) e não exibem as linhas características de emissão dos íons de terras raras. Os dados de analise térmica indicam que os complexos são termicamente estáveis até 325 graus Celsius e que apresentaram H2O absorvida da atmosfera. Os OLEDs fabricados e caracterizados neste trabalho foram de dois tipos: bicamadas e multicamadas.A1)ITO/NPB(25nm)/Li[TR](q)4](40nm)/Al(120nm);A2)ITO/NPB(25nm)/[Eu(DBM)3phen](20nm)/BCP(10nm)/Li[TR(q)4](20nm)/Al(120nm). Os OLEDs bicamadas apresentaram, em seus espectros de eletroluminescência, as bandas de emissão da (q) entre 520 ate 540nm. Os OLEDs multicamadas foram fabricados para testar a eficácia dos complexos Li[TR(q)4] como camadas transportadoras. Este trabalho evidenciou uma interessante dependência entre o pico máximo da emissão eletroluminescente e o raio iônico dos íons de TR. Os OLEDs baseados nos complexos Li[TR(q)4] apresentaram boas características quando comparadas com os OLEDs baseados Alq3, mostrando-se compostos promissores para o desenvolvimento de dispositivos orgânicos. / [en] The Alq3 is one of the most important organic semiconductors used as electron transporting and emitting material in organic electroluminescent devices (OLEDs). This work presents the investigation of the optical, electrochemical, electrical and morphological properties of three complexes based in ions of rare earth (RE) coordinated to 8-hydroxyquinoline (q), Li[RE(q)4] (RE equal La3more, Y3more and Lu3more). The UV-Vis absorption spectrum present the maximum absorption at: 382nm for Y3more/La3more complexes and 388nm for the Lu3more complex. The photoluminescence spectra of the complexes correspond to the emission of the (q) and does no exhibit characteristic lines of the rare earths ions. The thermal analysis data indicate that the complexes are thermally stable until 325 Celsius degrees and that showed H2O molecules absorbed from the atmosphere. The fabricated and characterized OLEDs in this work were of two types: bilayer and multilayer.A1)ITO/NPB(25nm)/Li[TR(q)4](40nm)/Al(120nm);A2)ITO/NPB(25nm)/[Eu(DBM)3phen](20nm)/BCP(10nm)/Li[TR(q)4](20nm)/Al(120nm). The bilayer OLEDs showed, in their electroluminescence spectra, the emission bands of the (q) between 520 until 540nm. The multilayer OLEDs were fabricated to test the efficiency of the complexes Li[TR(q)4] as transport layers. This work showed an interesting dependence between the EL emission peak and the ionic radius of the of RE ions. The OLEDs based on the Li[RE(q)4] complexes presented good characteristics when compared to the OLEDs based on Alq3, showing as promising compounds to the organic devices development.

Organic electronic devices are becoming commonplace in many academic and industrial materials laboratories, and commercial application of these technologies is underway. To maximize our fundamental understanding of organic electronics, a wide array of molecular frameworks is necessary, as it allows for a variety of optical and electronic properties to be systematically investigated. With the ability to further tune each individual scaffold via derivatization, access to a broad spectrum of interesting materials is possible. Of particular interest in the search for organic semiconducting materials are the cyclopenta-fused polyaromatic hydrocarbons, including those based on the fully conjugated indenofluorene (IF) system, which is comprised of five structural isomers. This dissertation represents my recent contributions to this area of research. Chapter I serves as a historical perspective on early indenofluorene research and a review of more current research on their synthesis and applications in organic electronic devices. Chapters II and III cover our early work developing the synthesis of the fully-reduced indeno[1,2-b]fluorene scaffold, with the latter of these chapters showing the first example of its application in an organic electronic device, a field effect transistor. Chapter IV demonstrates the first syntheses of fully-reduced indeno[2,1-c]fluorene derivatives. Chapter V expands our research to encompass isoelectronic heteroatomic derivatives of that same scaffold, introducing the fully-reduced diindeno[2,1-b:1',2'-d]thiophene scaffold and showing that our synthetic methodology also can be used to produce a quinoidal thiophene core. Chapter VI concludes with a review of the similarities between the indeno[2,1-c]fluorene and diindeno[2,1-b:1',2'-d]thiophene molecular architectures and introduces benzo[a]indeno[2,1-b]fluorene derivatives, demonstrating the first example of a fully-reduced indenofluorene that possesses a non-quinoidal core, illustrating that the quinoidal core is not a prerequisite for the strong electron affinities seen across the families of fully-reduced indenofluorenes. This dissertation encompasses previously published and unpublished co-authored material. / 2015-10-10

One of the major challenges in the field of organic semiconductors is to develop molecular design rules and processing routes which optimise the charge carrier mobility, whilst independently controlling the radiative and non-radiative processes. To date there has existed a seeming trade-off between charge carrier mobility and photoluminescence efficiency, which limits the development of some devices such as electrically pumped laser diodes. This thesis investigates fluorescence enhancement strategies for high-mobility polymer semiconductor systems and the mechanisms by which they currently display poor emission properties. Four independent approaches were taken and are detailed as follows. 1. Solubilising chain engineering It is shown that for the high mobility polymer poly(indacenodithiophene-co-benzothiadiazole), the addition of a phenyl- initiated side chain can enhance the solid-state fluorescence quantum yield, exciton lifetime and exciton diffusion length significantly in comparison to that without phenyl-addition. 2. Energy transfer to a highly fluorescent chromophore It is shown that for the high mobility polymer poly(indacenodithiophene-co-benzothiadiazole) efficient energy transfer to a more emissive squaraine dye molecule is possible despite fast non-radiative decay short exciton diffusion lengths. This results in a significant fluorescence enhancement, which in turn facilitates an order of magnitude increase of the efficiency of polymer light emitting diodes made from this material combination. 3. Energy gap engineering The well known Energy Gap Law predicts an increase in the non-radiative rate as the optical bandgap of an organic chromophore decreases in energy. In combination with this, almost all polymer semiconductors reported to date with high charge carrier mobility have low optical bandgaps. Therefore, molecular design principles which act to increase the optical bandgap of polymer semiconductors whilst retaining a high mobility were sought out. One specific system was successfully identified and showed a significant fluorescence enhancement compared to is predecessor poly(indacenodithiophene-co-benzothiadiazole) in both the solution and the solid state. It is found that the Frenkel exciton lifetime in this new system is a factor of four larger which also results in a significantly increased exciton diffusion length. An inter-chain electronic state is also identified and discussed. 4. Hydrogen substitution For some low-bandgap material systems such as erbium chromophores, high energy vibrational modes such as the C-H stretching mode can act as non-radiative pathways. The effect of hydrogen substitution with deuterium and fluorine was therefore investigated in a series of polythiophene derivative families. It was found that in the solid state, fluorescence and exciton lifetime enhancement occurred when the backbone hydrogen atoms were replaced with fluorine. However, evidence is given that this was not owing to the initial hypothesis, and is more likely owing to structural differences which occur in these substituted material systems.

<p>Over the last few decades, bulk-heterojunction organic photovoltaic devices comprising an intimately mixed donor-acceptor blend have gained serious attention due to their potential for being cheap, light weight, flexible and environmentally friendly. In this thesis, APFO-3/PCBM bulk-heterojunction based organic photovoltaic devices with an inverted layer sequence were investigated systematically. Doctor blade coating is a technique that is roll-to-roll compatible and cost efficient and has been used to fabricate the solar cells.</p><p>Initial studies focused on optimization of the electrodes. A thin film of the conductive polymer PEDOT:PSS was chosen to be the transparent anode. Different PEDOT:PSS films with respect to the film thickness and deposition temperature were characterized in terms of conductivity and transmission. Decent conductance and transmittance were obtained in the films deposited with wet film thickness setting of 35 μm, The cathode was fabricated from a metal bilayer comprising Al and Ti with an area about 1 cm², and the best-working cathodes contained a 70 nm thick Al layer covered by a thin Ti layer of about 10 -15 nm.</p><p>Optimized coating temperature and wet film thickness settings for the active layer and PEDOT:PSS layer were experimentally determined. The highest efficiency of the APFO-3/PCBM based inverted solar cells fabricated by doctor blading was 0.69%, which exceeded the efficiency of spin-coated inverted cells.</p><p>A higher efficiency (0.8 %) was achieved by adding a small amount of high molecular weight polystyrene to the active layer. Morphological changes after adding of the polystyrene were observed by optical microscopy and AFM. A coating temperature dependent phase separation of the APFO-3/PCBM/polystyrene blend was found.</p><p> </p>

<p>In this thesis, the microstructure of organic photovoltaic APFO-3:PC₆₁BM bulk-heterojunction blends was examined. Earlier studies have focused on the microstructure after spin coating. This thesis aims to give a better insight into microstructural degradation as the films are annealed above the glass transition temperature, T_g, and the mixture approaches thermodynamic equilibrium. Electro- and photoluminescence studies indicate that the polymer and PC₆₁BM are intermixed on a scale shorter than the exciton diffusion length of 10 nm, even when annealed above T_g. The temperature stability of APFO-3:PC₆₁BM was also investigated with respect to the molecular weight of the polymer. The photovoltaic performance of these blends was found to be stable up to temperatures approaching the glass transition temperature, especially if a high molecular-weight APFO-3 grade was used.</p><p> </p><p>The crystallization of PC₆₁BM was also investigated. Above T_g, PC₆₁BM crystallization was found to commence, albeit slowly at temperatures close to T_g. At elevated temperatures instead, micrometer sized crystals were observed to form. It was also noted that illumination while annealing APFO-3:PC₆₁BM thin films above T_g affected PC₆₁BM crystallization, the origin of which is so far unclear although chemical degradation could be largely excluded.</p>

In this thesis, the microstructure of organic photovoltaic APFO-3:PC61BM bulk-heterojunction blends was examined. Earlier studies have focused on the microstructure after spin coating. This thesis aims to give a better insight into microstructural degradation as the films are annealed above the glass transition temperature, Tg, and the mixture approaches thermodynamic equilibrium. Electro- and photoluminescence studies indicate that the polymer and PC61BM are intermixed on a scale shorter than the exciton diffusion length of 10 nm, even when annealed above Tg. The temperature stability of APFO-3:PC61BM was also investigated with respect to the molecular weight of the polymer. The photovoltaic performance of these blends was found to be stable up to temperatures approaching the glass transition temperature, especially if a high molecular-weight APFO-3 grade was used.   The crystallization of PC61BM was also investigated. Above Tg, PC61BM crystallization was found to commence, albeit slowly at temperatures close to Tg. At elevated temperatures instead, micrometer sized crystals were observed to form. It was also noted that illumination while annealing APFO-3:PC61BM thin films above Tg affected PC61BM crystallization, the origin of which is so far unclear although chemical degradation could be largely excluded.

Over the last few decades, bulk-heterojunction organic photovoltaic devices comprising an intimately mixed donor-acceptor blend have gained serious attention due to their potential for being cheap, light weight, flexible and environmentally friendly. In this thesis, APFO-3/PCBM bulk-heterojunction based organic photovoltaic devices with an inverted layer sequence were investigated systematically. Doctor blade coating is a technique that is roll-to-roll compatible and cost efficient and has been used to fabricate the solar cells. Initial studies focused on optimization of the electrodes. A thin film of the conductive polymer PEDOT:PSS was chosen to be the transparent anode. Different PEDOT:PSS films with respect to the film thickness and deposition temperature were characterized in terms of conductivity and transmission. Decent conductance and transmittance were obtained in the films deposited with wet film thickness setting of 35 μm, The cathode was fabricated from a metal bilayer comprising Al and Ti with an area about 1 cm2, and the best-working cathodes contained a 70 nm thick Al layer covered by a thin Ti layer of about 10 -15 nm. Optimized coating temperature and wet film thickness settings for the active layer and PEDOT:PSS layer were experimentally determined. The highest efficiency of the APFO-3/PCBM based inverted solar cells fabricated by doctor blading was 0.69%, which exceeded the efficiency of spin-coated inverted cells. A higher efficiency (0.8 %) was achieved by adding a small amount of high molecular weight polystyrene to the active layer. Morphological changes after adding of the polystyrene were observed by optical microscopy and AFM. A coating temperature dependent phase separation of the APFO-3/PCBM/polystyrene blend was found.

In this thesis, we study the physical properties of doped organic semiconductors. We first demonstrate the impact of doping on C60 films. In contrast to previous reports for organic thin films, the n-doped C60 films show a decrease of mobility with increasing doping levels; i.e., they follow the well-known Matthiessen rule which is generally observed in inorganic semiconductors. Using further strong organic donors and acceptors, we realize p-i-n homojunctions of several organic matrices: zinc-phthalocyanine, pentacene, and an iridium-complex TER004. We observe stable and reproducible diode characteristics, which can be described by the standard Shockley theory with an exception concerning the temperature dependence of the diode parameters. The current-voltage characteristics of the pentacene homojunctions under illuminated conditions indicate that the thermodynamic limitation of the open-circuit voltage is determined by the built-in voltage of 1.65 V, and that the recombination process is influenced by the distinct charge transport properties of electrons and holes. The very high built-in voltage of 2.2 V in the TER004 homojunction allows a red phosphorescent homo-OLED, which shows visible emission around 650 nm with low operation voltage. We examine the charge balance status in the homojunction structure, revealing that TER004 has superior electron transport properties.