Organic semiconductors are envisioned to have widespread applications in flexible displays, radio-frequency identification (RFID) tags, bio- and chem-sensors, as well as organic solar cells. Polymer semiconductors are particularly suitable for the low-cost manufacture of organic electronics using printing techniques due to their excellent solution processability and mechanical properties. This work focuses on the development of two novel building blocks, IBDF and DTA, which can be used for the construction of high performance organic thin film transistors (OTFTs) and organic photovoltaics (OPVs). Two copolymers, P6-IBDF-T and P5-IBDF-T, and a homopolymer P6-IBDF were prepared using the IBDF building block. Copolymer P6-IBDF-T has been prepared via the Stille-coupling polymerization. This polymer exhibits a small band gap of 1.36 eV with HOMO/LUMO energy level of -5.69 eV/-4.43 eV. P6-IBDF-T showed stable electron transport performance in encapsulated thin film transistors and ambipolar transport performance in non-encapsulated TFTs. Balanced hole/electron mobilities of up to 8.2 ??10-3/1.0 ??10-2 cm2V-1s-1 was achieved in bottom-contact, bottom-gate organic thin film transistors. In addition, the broad absorption of the polymer over the UV-Vis range suggested that this polymer is suitable for applications in solar cells. The effect of conjugation on mobility and UV-vis spectra of the polymer was studied by comparing P5-IBDF-T with P6-IBDF-T. The ideal of indirect electron transition was proposed to explain the difference between UV-Vis light absorption spectra for these two polymers. DTA building block was used to construct four D-A copolymers, namely PDTA-T, PDTA-BT, PDAT-BTV, and PDTA-TT. These polymers were characterized by UV-Vis, CV, DSC, TGA, AFM and XRD. Device performance was also investigated on OTFTs. The device performance of DTA based polymer increased as the area of electron donor increase from T in PDTA-T to BTV in PDTA-BTV. PDTA-BTV exhibits hole mobility of 1.3??10-3 cm2 V-1 s-1 with Ion/Ioff value of ~103-4 in bottom-contact, bottom-gate organic thin film transistors. All DTA based copolymers exhibited small optical bandgaps (1.18 ??? 1.27 eV) and required none or moderate thermal treatment during fabrication process. These make them promising candidates for cost-effective OPV applications.

This dissertation consists of six chapters: In the first chapter, electrical and material properties and charge transport in organic semiconductors and graphene based field-effect transistors (FETs) are introduced. In the second chapter, device architectures of indenofluorene-phenanthrene copolymer based thin-film transistors (TFTs) are discussed. The combination of recessed source/drain and surface treatments on electrical contact and low-voltage-operated TFTs with solution-processed high-k dielectric are investigated. In the third chapter, device physics and charge transport of diketopyrrolopyrrole-naphthalene copolymer based TFTs are discussed. Top-gate TFTs with the polymer dielectric exhibit mobilities of ~1 cm2/V-s and charge transport measurements in steady-state and under non-quasi-static conditions reveal device physics in dual-gate configuration. In the fourth chapter, device characteristics and charge transport in ambipolar diketopyrrolopyrrole-benzothiadiazole copolymer based TFTs are focused. The ambipolar polymer TFTs possess balanced electron and hole mobilities which are both > 0.5 cm2/V-s. The trap density of states is calculated using two analytical methods developed by Lang et al. and Kalb and Batlogg. In the fifth chapter, charge transport of diketopyrrolopyrrole-thiophene copolymer based TFTs employing 4-point-probe configuration is studied. Such polymer TFTs possess the mobilities of up to 3 cm2/V-s. The activation energy as a function of carrier concentration represents multiple trapping and thermally release model or Monroe-type model of charge transport. In the sixth chapter, transformation of electrical characteristics of graphene FETs with an interacting capping layer of fluoropolymers and pi-conjugated organic semiconductors is investigated. The electrical properties of graphene by wafer-scale chemical vapor deposition can be favorably tuned by fluorocarbon capping methods. / text

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.

This thesis reports the light emission in ion gel gated, thin film organic semiconductor transistors and investigates the light emission mechanism behind these devices. We report that ion gel gated organic polymer semiconductor transistors emit light when the drain source voltage is swept slightly beyond the energy gap of the polymer divided by the elementary charge (Vds > Eg/e). In particular, the light emission in poly(9,9'-dioctylfluorene-co-benzothiadiazole)(F8BT) polymer semiconductor, with 1-ethyl-3-methylimidazoliumbis (trifluoromethylsulfonyl)imide/ poly(styrene-block-ethylene oxide-block-styrene) (EMIM TFSI/ SOS) ion gel as dielectric material is reported. The current-voltage characteristics corresponding to the light emission, where the systematic increase of the drain current, correlated with light emission is reported. In low voltage regime, (Vds < Eg/e), well saturated transistor characteristics are observed. By charge modulation spectroscopy (CMS) study we show that there is a prominent electrochemical doping occurring with gate voltages. Further, owing to the movement of ions with voltages,irrespective of the location of electrodes, we show that the ion gel, bilayer planar devices emit light in Vds > Eg/e regime (without any gate voltages), at room temperature. Based on thelocation of the recombination zone in the proximity of electron injecting electrode and CMS results showing prominent di ffusion of negative ions into the polymer layer, we conclude that the light emitting mechanism is akin to light emitting electrochemical cells (LECs). Even in the the transistor regime, where Vds << Eg/e, with the signatures of increasing drain current for fixed Vg and Vds values, we show that the transistor can not be of purely electrostatic operation alone. We study the fluorescence quenching of an operating bilayer device under a constant bias over a period of time and compare the results with the electroluminescence of the device and show that the formation of the p-n junction within the polymer layer due to the penetrated ions from the gel dielectric into the polymer semiconductor layer on the application of the voltage is the cause behind the light emission. We show that diffusivity of the cation (EMIM) is very low compared to the anion (TFSI). This is consistent with the fact that the recombination zone is near theelectron injecting electrode in these devices. We have developed a theoretical model for the ions movement within the semiconductor polymer matrix governed by both diffusion and drift independently, for the bilayer, polymer ion gel planar, light emitting electrochemical cells. We have further developed a 2- dimensional numerical modelbased on the theoretical model and have compared the results of the numerical model with theresults of a fluorescence probing of the bilayer device with time, at constant potential across the bilayer LEC and report that the drift coefficient of 1x10⁻¹³ cm²/V.s and a diffusion coefficient of 1 x 10⁻¹⁵cm²/V.s for TFSI ions in F8BT matrix.