Solution-processed organic field effect transistors (OFETs) have emerged in recent years as promising contenders to be part of electronic and optoelectronic circuits owing to their compatibility with low-cost high throughput roll-to-roll manufacturing technology. The stringent performance requirements for OFETs in terms of carrier mobility, switching speed, turn-on voltage and uniformity over large areas require the performance of single crystal-based OFETs, but these suffer from major scale-up challenges. To achieve device performance approaching that of single crystals with scalable, high throughput and industry-compatible solution coating of OFETs requires understanding and ultimately controlling the crystallization of organic semiconductors (OSCs), and producing very low defect-density thin films. In this thesis, we develop an understanding of the process-structure-property-performance relationship in OSCs that bring fresh insights into the nature of solution crystallization and lead to novel ways to control OSC crystallization, and finally help achieve fabrication of high-performance OFETs by scalable, high throughput and industry-compatible blade coating method. We probe the solution crystallization of OSCs by employing a suite of ex & in situ characterization techniques. This leads us to an important finding that OSC molecules aggregate to form a dense amorphous intermediate state and nucleation happens from this intermediate state during blade coating under a wide window of coating conditions. This phenomenon resembles the so-called two-step nucleation model. Two-step nucleation mediates the crystallization of a wide range of natural and synthetic products ranging from soft materials, such as proteins, biominerals, colloids and pharmaceutical molecules, to inorganic compounds. We go on to show that this nucleation mechanism is generally applicable to achieve formation of high-quality polycrystalline films in a variety of small molecule OSCs and their polymer blends. This phenomenon results in highly textured and well-connected domains, which exhibit reduced interfacial and bulk trap-state densities, helping raise the carrier mobility by one to two orders of magnitude in OFETs in comparison to direct nucleation. We extend the understanding developed for solution crystallization of various acenes and thiophene-based small molecule OSCs to the high-performance benzothieno-benzothiophene (BTBT) based small molecule OSCs. On this end, we develop protocols to fabricate high-quality thin films of BTBT based OSCs by blade coating at industrially compatible coating speeds (>100 mms-1). These films show massive single-domains with very few apparent defects when crystallized via multiple liquid-crystalline phases in two-step nucleation conditions, resulting in an average carrier mobility of ~10 cm2V-1s-1. To sum up, this thesis develops an understanding of OSC solution crystallization and efficient protocols to control polycrystalline thin film quality for high-performance OFETs. These protocols involve a combination of two-step nucleation pathway, solvent mixtures, polymer blends and device-manufacturing conditions. Our efforts enable to realize high-performance OFETs based on high-quality polycrystalline OSC thin films at industry-compatible conditions.

Les transistors organiques à effet de champ (OFETs) dans lesquels le transport des charges se fait à travers un film mince de molécules organiques représentent une transformation de la technologie des transistors à effet de champ au regard de la technologie au silicium. Ils permettent notamment d’envisager le développement d’une électronique flexible à bas coût. Ce travail porte sur la synthèse, l’étude et l’utilisation en tant que couche active dans des OFETs de type n de couples d’isomères para- et méta-indacénodithiophènes (para- et méta-IDT) appauvris en électrons inédits. Une introduction aux OFETs de type n est tout d’abord présentée. Elle est suivie par la présentation de la synthèse des dérivés IDT et de l’analyse comparée de leurs propriétés physico-chimiques. La fabrication des OFETs, leur caractérisation et l’optimisation de leur architecture est enfin décrite, leurs performances montrant l’intérêt des IDTs pour les OFETs de type n. Différentes fonctionnalisations menant à des IDTs d’architecture 3π-2spiro sont également synthétisées afin d’étudier les propriétés intrinsèques de ces dérivés π-conjugués et d’envisager leur incorporation comme matrice hôte dans des diodes électrophosphorescentes organiques. / Organic Field Effect Transistors (OFETs), in which the charge transport is carried through a thin film made of organic molecules represent a transformation of the FET technology regarding that based on Silicon. They offer in particular the possibility to manufacture low cost flexible electronics. This work is focused on the synthesis, the study and the use as active layer in n-type OFETs of novel, electron poor, couples of para- and meta-indacenodithiophenes isomers (para- and meta-IDT). First of all, an introduction to the field of n-type OFETs is presented, followed by the presentation of the synthesis of the IDT derivatives and the comparative analysis of their properties. Finally, the fabrication of the OFETs, their characterization and the optimization of their architecture is described. The performances recorded attest that these derivatives are of great interest for the n-type OFETs. Different 3π-2spiro IDT derivatives are also presented in order to study the IDTs intrinsic properties and to envisage their incorporation as host in phosphorescent organic light-emitting diodes.

Organic phototransistors (OPTs) can enable essential applications, such as nonvolatile memory, artificial synapses, and photosensors in next-generation optical communication and wearable electronics. Among these applications, nonvolatile OPT memories are particularly promising, as they can retain captured visual information for extended periods, making them valuable for data storage, image and video processing applications. The capability of storing multi-bit information, which provides a low-cost way to increase the memory density per unit cell area, is one of the most critical challenges of memory products. In this work, we explore different solution-processible electrets to obtain highly sensitive phototransistor memory devices. Different planar heterojunctions, including small molecule/small molecule and small molecule/polymer, are used to fabricate OPT memories. Additionally, we explore the feasibility of producing polymer/polymer planar heterojunctions through printing processes. Firstly, OPT memories that can be programmed with white light and erased by applying a negative voltage are fabricated with a planar heterojunction of a nonconductive nanographene layer and a semiconducting layer of 2,9-didecyldinaphtho[2,3-b:2’,3’-f]thieno[3,2-b]thiophene (C10-DNTT). We systematically study the optical and memory characteristics of devices with an 8 nm nanographene (NG) layer. The photosensitivity of such devices can be as high as 3.4×105. The memory also shows quite good endurance and data-storing stability; an endurance of 100 write-read-erase-read (WRER) cycles and 1.5×105 s retention time are obtained. The thickness of the NG layer has a considerable influence on the performance of fabricated devices. The results suggest that devices with a thicker NG layer are more sensitive to weak light. In comparison, devices with a relatively thin NG layer are found to be promising for multi-bit photo memory devices. Secondly, we fabricate OPT memories by replacing the nanographene layer with a commercially available semiconducting polymer, namely Poly(2,5-bis(2-octyldodecyl)-3,6-di(pyridin-2-yl)-pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione-alt-2,2’-bithiophene) (PDBPyBT). This polymer possesses a narrow bandgap and exhibits a broad range of light absorption, spanning from ultraviolet (UV) to red light wavelengths. As a result, the fabricated devices are capable of responding to a broad spectrum of light colors. The light response of these devices is investigated in terms of their reaction to different colors of light. Also, devices with varying thicknesses of the PDBPyBT layer are fabricated and studied. The results indicate that all of the fabricated devices demonstrate multi-bit programming properties, and the devices incorporating a thin, ribbon-structured PDBPyBT layer are particularly well-suited for applications as light dosimeters. Moreover, the results highlight that both the C10-DNTT and the PDBPyBT layer function as photo exciton generation and charge-trapping layers. Last, we seek to fabricate cost-effective organic multilayer devices through a solution-processing approach, eliminating the need for orthogonal solvents. We observe a crosslinking effect in the thin films caused by thermal annealing without using any crosslinker. Remarkably, this effect is found to be universal for several commercial semiconducting polymers investigated in our study. Following annealing at 200 ºC or higher temperatures, the thin films exhibit enhanced stability against the original solvent. Various analytical techniques are employed to examine the thin films to gain insights into the microstructural changes. Our results suggest that the observed crosslinking effect is predominantly attributed to a physical transformation, whereby the films became more crystalline after annealing at relatively high temperatures. To further explore the feasibility of fabricating multilayer devices, we simulate the construction of multilayer devices by top-gate-bottom-contact (TGBC) devices using the same solvent for the polymer dielectric layer and the semiconducting layer. We also fabricated planar polymer/polymer heterojunction via this method. Encouragingly, this approach demonstrated that thermal annealing could work as a straightforward and promising method for producing cost-effective organic multilayer devices, e.g., fully solution-processed diodes, functional transistors, and solar cells.:Abstract iii Contents vii 1 Introduction 1 1.1 Motivation 1 1.2 Organic semiconductor 2 1.2.1 Atom orbitals and molecular orbitals 2 1.2.2 Energy levels in solid 5 1.2.3 Fermi level 6 1.2.4 Band bending 7 1.2.5 From orbital to states 8 1.2.6 Organic semiconductor materials 9 1.2.7 Nanographene 10 1.2.8 Charge carrier transport in organic semiconductors 11 1.3 Organic field-effect transistors (OFET) 11 1.3.1 OFET architectures 12 1.3.2 OFET operation principle 12 1.3.3 OFET performance parameters 14 1.3.4 OFET memory 17 1.4 Optical electronics 20 1.4.1 Exciton pair generation. 20 1.4.2 Photoelectronic devices 21 1.4.3 Phototransistor devices 22 1.5 Phototransistor memories 23 1.5.1 Working mechanism of phototransistor memories 23 1.5.2 Phototransistor memory architecture 24 1.5.3 State-of-the-art organic phototransistor memory 25 1.6 Objective and outline 27 2 Materials and methods 29 2.1 Materials 29 2.2 Device fabrication 30 2.2.1 Substrate cleaning 30 2.2.2 Solution shearing 30 2.2.3 Thermal vapor deposition 31 2.3 Characterization 31 2.3.1 Thin film characterization 31 2.3.2 Current voltage characteristics 35 2.3.3 Capacitance 36 3 C10-DNTT/NG planar heterojunction phototransistor memories 37 3.1 Introduction 37 3.2 Thin films 39 3.2.1 Film and device fabrication 39 3.2.2 Characterization of thin films 39 3.3 Transfer characteristics under light 41 3.3.1 Writing process 41 3.3.2 Erasing process 48 3.3.3 C10-DNTT-only devices 51 3.4 Summary of working principle 52 3.5 Output characteristics and evaluation of the optical properties 52 3.6 Memory properties of NG-based OPT memory devices 55 3.7 Devices with different NG thicknesses 56 3.7.1 The impact of NG thickness 56 3.7.2 Devices fabricated from 0.05 mg ml-1 NG solution 60 3.8 Conclusion 64 4 C10-DNTT/PDBPyBT heterojunction phototransistor memories 67 4.1 Introduction 67 4.2 Device Architecture 68 4.3 Physical characterization of PDBPyBT and C10-DNTT thin films 69 4.4 Performance of devices with a thick PDBPyBT layer 72 4.4.1 Erasing and programming process 72 4.4.2 Response to different colors of light 78 4.5 Variation of PDBPyBT thickness 80 4.5.1 Transfer characteristics 80 4.5.2 Morphology of C10-DNTT 85 4.5.3 Output characteristics 86 4.5.4 Multi-level programming test 86 4.6 Comparison of the devices 92 4.7 Summary 93 5 Organic multilayer devices fabricated via thermal annealing 95 5.1 Introduction 95 5.2 Film Fabrication 97 5.3 Study on thin films 97 5.3.1 Thickness changes 97 5.3.2 Characterization of the thin films 99 5.3.3 Impact of re-annealing 107 5.3.4 Other semiconducting polymers 108 5.4 Discussion of the working mechanism 110 5.5 Impact of thermal annealing on devices’ performance 111 5.5.1 BGTC devices fabrication 111 5.5.2 TGBC devices fabrication 113 5.6 Planar heterojunction devices via solution processing 116 5.7 Conclusion 117 6 Conclusions and outlook 119 6.1 Conclusions 119 6.2 Outlook 120 Bibliography 123 List of Figures 143 List of Tables 155 List of abbreviations 157 Appendix A 159 Appendix B 165 B1.1 Introduction 165 B1.2 Devices with a 7 nm shear coated Al2O3 dielectric 166 B1.2.1 Normal-sized channel devices 166 B1.2.2 Ultra-wide channel devices 167 B1.3 Devices with a 30 nm ALD Al2O3 dielectric 169 B1.3.1 Normal-sized channel devices 169 B1.3.2 Ultra-wide channel devices 170 B1.4 Ferroelectric organic phototransistor devices 172 B1.4.1 Dielectric layer 172 B1.4.2 Devices with 10 nm HZO 173 B1.4.3 Devices with 30 nm HZO 175 Conclusion 176 Publications 177 Acknowledgment 179

Esta tese tem por objetivo o desenvolvimento de metodologias eficientes e de baixo custo para ajustar as propriedades elétricas de OFETs de canal p e de canal n, a fim de possibilitar a fabricação do circuito complementar orgânico, semelhante a uma estrutura CMOS. O desempenho do circuito complementar fabricado foi otimizado, e também foi confeccionado por impressão um OFETs de canal operando em baixas tensões. Para a fabricação do CMOS orgânico foi proposto um método baseado na seleção adequada do solvente da camada dielétrica para ajustar o desempenho elétrico dos OFETs de canal p e de canal n. Os solventes, MEK, nBA e DMSO foram selecionados para a dissolução do PMMA por apresentarem diferenças nos valores de momento de dipolo, de ponto de ebulição e de graus de ortogonalidade em relação as camadas semicondutoras de P3HT e de P(NDI2OD-T2) dos OFETs. A análise dos resultados dos OFETs de canal p e de canal n demonstrou que a metodologia proposta é adequada tanto para o ajuste das propriedades elétricas destes dispositivos quanto para a otimização do desempenho dos mesmos. Os melhores desempenhos elétricos para os OFETs de canal p e de canal n foram obtidos quando utilizados o DMSO e o MEK como solventes do PMMA, respectivamente, devido à perfeita ortogonalidade destes solventes em relação às camadas semicondutoras. Os OFETs de canal p que utilizaram o DMSO e os OFETs de canal n que utilizaram o nBA foram os que apresentaram desempenhos elétricos semelhantes, sendo portanto aplicados na fabricação do CMOS. Valores de ganho entre 6,8 e 7,8 e de margem de ruído entre 28,3 V e 34,5 V foram obtidos para inversores complementares fabricados nesta etapa do trabalho. OFETs de canal p utilizando uma blenda de PTAA: diF TES ADT como camada semicondutora, o PEDOT:PSS como eletrodos dreno/fonte e o P(VDF-TrFE-CFE) como camada dielétrica também foram fabricados neste trabalho. A técnica de blade-coating foi utilizada para a deposição dos eletrodos dreno/fonte e da camada semicondutora, ao passo que a técnica de spray-coating foi utilizada para a deposição da camada dielétrica. Da análise dos resultados foi possível inferir que a utilização de um dielétrico com elevada constante dielétrica (K), como o P(VDF-TrFE-CFE), possibilita o funcionamento dos transistores a baixas tensões (≤ 8 V), porém com valores de mobilidade reduzidos devido à elevada desordem dipolar na interface provocada por este dielétrico. Para minimizar esses efeitos, uma fina camada de um polímero fluorado foi depositada entre a camada semicondutora e a dielétrica pela técnica de blade-coating, constituindo assim uma bicamada dielétrica nos OFETs. Dos resultados das medidas elétricas dos OFETs constituídos pela bicamada dielétrica foi observada permanência do funcionamento destes dispositivos a tensões inferiores a 8 V com desempenho elétricos superiores a resultados já publicados na literatura. Por fim, inversores lógicos unipolares com transistores de carga foram fabricados com os OFETs que utilizaram a bicamada dielétrica, sendo obtidos valores de ganho entre 1,2 e 1,6 e de margem de ruído entre 56% e 68,5% de ½ VDD. / This thesis aimed to develop an efficient and low cost method to adjust the electrical properties of p- and n-channel OFETs to allow us to build an organic CMOS and the optimization of printed p-channel OFETs to work at low voltages. We proposed a method to fabricate the organic CMOS, based on the careful selection of dielectric solvent, which was adjusted to obtain the best performance of p- and n-channel OFETs. The dielectric solvents as MEK, nBA and DMSO were selected to dissolve the PMMA dielectric polymer due their different physical properties as dipole moment and boiling point and because they showed slightly different degrees of orthogonality to the P3HT and P(NDI2OD-T2) semiconductor layers of the OFETs. The results showed that the careful selection of the dielectric solvent not only allows to tune the electrical characteristics of the p- and n-channel OFETs, but also to improve the performance of these devices. The best performances were achieved when DMSO and MEK were used as dielectric solvents of the p and n-channel OFETs, respectively, as result of the perfectly orthogonality of these solvents to the semiconductor layers. P-channel OFETs using DMSO and n-channel OFETs using nBA showed similar electrical characteristics and thus, they were used to construct the organic CMOS. The organic complementary inverters showed high gain and noise margin values in the range of 6,8 to 7,8 and 28,3 V to 34,5 V, respectively. Printed p-channel OFETs were also fabricated, in which the blend PTAA:diF TES ADT was used as semiconductor channel, PEDOT:PSS as the drain/source electrodes and P(VDF-TrFE-CFE) as the dielectric layer. The blade-coating technique was used to deposit the source/drain electrodes and the semiconductor layer, while the spray-coating technique was used to deposit the dielectric layer. It was observed that using high-k dielectric as P(VDF-TrFE-CFE) enable to reduce the operating voltage of the OFETs (≤8 V), however, this high-k dielectric also reduced the field effect mobility due the dipolar disorder at the semiconductor/dielectric interface. To minimize the dipolar issue at the interface, we inserted a thin fluoropolymer dielectric layer by blade-coating between the semiconductor and the high-k dielectric layers, thus constituting a dielectric bilayer on the OFETs. From the electrical measurements of the OFETs with the dielectric bilayer, it was observed that the devices were still working at 8 V and they also showed better performance in comparison to results already published. Finally, organic unipolar inverters with load transistors were fabricated using the p-channel OFETs with the dielectric bilayer and they showed reasonable performance, with gain and noise margin in the range of 1,2 to 1,6 and 56% e 68,5% of ½ VDD, respectively.

Esta tese tem por objetivo o desenvolvimento de metodologias eficientes e de baixo custo para ajustar as propriedades elétricas de OFETs de canal p e de canal n, a fim de possibilitar a fabricação do circuito complementar orgânico, semelhante a uma estrutura CMOS. O desempenho do circuito complementar fabricado foi otimizado, e também foi confeccionado por impressão um OFETs de canal operando em baixas tensões. Para a fabricação do CMOS orgânico foi proposto um método baseado na seleção adequada do solvente da camada dielétrica para ajustar o desempenho elétrico dos OFETs de canal p e de canal n. Os solventes, MEK, nBA e DMSO foram selecionados para a dissolução do PMMA por apresentarem diferenças nos valores de momento de dipolo, de ponto de ebulição e de graus de ortogonalidade em relação as camadas semicondutoras de P3HT e de P(NDI2OD-T2) dos OFETs. A análise dos resultados dos OFETs de canal p e de canal n demonstrou que a metodologia proposta é adequada tanto para o ajuste das propriedades elétricas destes dispositivos quanto para a otimização do desempenho dos mesmos. Os melhores desempenhos elétricos para os OFETs de canal p e de canal n foram obtidos quando utilizados o DMSO e o MEK como solventes do PMMA, respectivamente, devido à perfeita ortogonalidade destes solventes em relação às camadas semicondutoras. Os OFETs de canal p que utilizaram o DMSO e os OFETs de canal n que utilizaram o nBA foram os que apresentaram desempenhos elétricos semelhantes, sendo portanto aplicados na fabricação do CMOS. Valores de ganho entre 6,8 e 7,8 e de margem de ruído entre 28,3 V e 34,5 V foram obtidos para inversores complementares fabricados nesta etapa do trabalho. OFETs de canal p utilizando uma blenda de PTAA: diF TES ADT como camada semicondutora, o PEDOT:PSS como eletrodos dreno/fonte e o P(VDF-TrFE-CFE) como camada dielétrica também foram fabricados neste trabalho. A técnica de blade-coating foi utilizada para a deposição dos eletrodos dreno/fonte e da camada semicondutora, ao passo que a técnica de spray-coating foi utilizada para a deposição da camada dielétrica. Da análise dos resultados foi possível inferir que a utilização de um dielétrico com elevada constante dielétrica (K), como o P(VDF-TrFE-CFE), possibilita o funcionamento dos transistores a baixas tensões (≤ 8 V), porém com valores de mobilidade reduzidos devido à elevada desordem dipolar na interface provocada por este dielétrico. Para minimizar esses efeitos, uma fina camada de um polímero fluorado foi depositada entre a camada semicondutora e a dielétrica pela técnica de blade-coating, constituindo assim uma bicamada dielétrica nos OFETs. Dos resultados das medidas elétricas dos OFETs constituídos pela bicamada dielétrica foi observada permanência do funcionamento destes dispositivos a tensões inferiores a 8 V com desempenho elétricos superiores a resultados já publicados na literatura. Por fim, inversores lógicos unipolares com transistores de carga foram fabricados com os OFETs que utilizaram a bicamada dielétrica, sendo obtidos valores de ganho entre 1,2 e 1,6 e de margem de ruído entre 56% e 68,5% de ½ VDD. / This thesis aimed to develop an efficient and low cost method to adjust the electrical properties of p- and n-channel OFETs to allow us to build an organic CMOS and the optimization of printed p-channel OFETs to work at low voltages. We proposed a method to fabricate the organic CMOS, based on the careful selection of dielectric solvent, which was adjusted to obtain the best performance of p- and n-channel OFETs. The dielectric solvents as MEK, nBA and DMSO were selected to dissolve the PMMA dielectric polymer due their different physical properties as dipole moment and boiling point and because they showed slightly different degrees of orthogonality to the P3HT and P(NDI2OD-T2) semiconductor layers of the OFETs. The results showed that the careful selection of the dielectric solvent not only allows to tune the electrical characteristics of the p- and n-channel OFETs, but also to improve the performance of these devices. The best performances were achieved when DMSO and MEK were used as dielectric solvents of the p and n-channel OFETs, respectively, as result of the perfectly orthogonality of these solvents to the semiconductor layers. P-channel OFETs using DMSO and n-channel OFETs using nBA showed similar electrical characteristics and thus, they were used to construct the organic CMOS. The organic complementary inverters showed high gain and noise margin values in the range of 6,8 to 7,8 and 28,3 V to 34,5 V, respectively. Printed p-channel OFETs were also fabricated, in which the blend PTAA:diF TES ADT was used as semiconductor channel, PEDOT:PSS as the drain/source electrodes and P(VDF-TrFE-CFE) as the dielectric layer. The blade-coating technique was used to deposit the source/drain electrodes and the semiconductor layer, while the spray-coating technique was used to deposit the dielectric layer. It was observed that using high-k dielectric as P(VDF-TrFE-CFE) enable to reduce the operating voltage of the OFETs (≤8 V), however, this high-k dielectric also reduced the field effect mobility due the dipolar disorder at the semiconductor/dielectric interface. To minimize the dipolar issue at the interface, we inserted a thin fluoropolymer dielectric layer by blade-coating between the semiconductor and the high-k dielectric layers, thus constituting a dielectric bilayer on the OFETs. From the electrical measurements of the OFETs with the dielectric bilayer, it was observed that the devices were still working at 8 V and they also showed better performance in comparison to results already published. Finally, organic unipolar inverters with load transistors were fabricated using the p-channel OFETs with the dielectric bilayer and they showed reasonable performance, with gain and noise margin in the range of 1,2 to 1,6 and 56% e 68,5% of ½ VDD, respectively.

Organic semiconductors are widely studied as potential active components for consumer electronics due largely to their easily tuned properties and the promise of lower-cost solution-based processing technology. Imide-functionalized organic small molecule compounds have been one of the more important and studied organic semiconductors. However, very few imide-functionalized conjugated polymers have been reported in the literature. The body of this dissertation focuses on the synthesis, structure-property and device studies of imide-functionalized conjugated polymers. Reasons for choosing arylene imides as polymer building blocks include: a) they impart low-lying LUMOs to polymers, allowing band-gap engineering through choice of comonomers with variable electron-donating ability; b) imide-nitrogens provide points to attach side chains to manipulate solubility and solid-state packing; c) they are easily prepared. Structure-property studies include electrochemical measurements, UV-Vis absorption spectroscopy, differential scanning calorimetry (DSC), x-ray diffraction, and in some cases evaluation as active components in field-effect transistors (OFETs) and photovoltaic devices (PVDs). The published method to synthesize 3,6-dibromo-pyromellitic bisimides (PMBI) was streamlined and poly(phenylene ethynylene)s (PPEs) with variable band gaps were prepared from them (Chapter 2). As noted in all the chapters, electrochemical and optical measurements reveal that the LUMO of the polymers is indeed dictated by the arylene imide, while the HOMO, and therefore the optical energy gap is controlled through varying the electron donor monomer. Intramolecular hydrogen bonding was employed for increasing backbone coplanarity and therefore the polymer could have higher conjugation. One of these polymers demonstrated the narrowest band gap (1.50 eV) for any published PPE. Chapter 3 describes the first published conjugated copolymers from naphthalene bisimides (NBI), here using thiophene-based comonomers as donor units. Polymers with high molecular weight and decent solubility were obtained by choosing appropriate side chains. The optical energy gaps could be tuned across the visible and into the near IR. Preliminary OFET studies revealed electron mobility as high as ~0.01 cm2/Vs. One low band gap polymer provided OFETs with electron mobility of ~0.04 cm2/Vs and hole mobility of ~0.003 cm2/Vs, which is also among the highest mobilities of ambipolar polymeric semiconductors. Using the same approach as in Chapter 3, phthalimide-based monomers were incorporated into polymer backbones for developing new high performance p-type polymer semiconductors for OFETs and PVDs (Chapter 4). Some analogues based on benzothiadiazole, PMBI, and thiophene imides as acceptors were prepared for comparison. Again, high molecular weight, soluble polymers with band gaps spanning the visible and into the near IR were obtained. OFETs from one of the polymers yielded hole mobility ~0.3 cm2/Vs under ambient atmosphere without post-processing thermal annealing, which places it squarely within the state-of-the-art for conjugated polymers. Due to the high mobility and low band gap, this polymer also leads to PVDs with moderately good power conversion efficiency (PCE: ~2%).

Despite significant advances in the field of organic electronic devices, a complete and thorough theoretical understanding of their operation is still missing. This study aims to deepen the understanding of the underlying physics of organic field-effect transistors (OFETs) through analytical modeling, numerical device simulations and experimental validations of contact-induced performance improvements and traps. The thesis presents a comprehensive methodology for reliable parameter extraction for the contact resistance of OFETs using conventional extraction methods originally developed for silicon-based transistors. A benchmarking strategy is proposed for accurate and reliable parameter extraction, involving a comparative study of different extraction techniques to ensure the most precise results. The study investigates the experimentally proven performance gain of OFETs with contact engineering on oxidized metal electrodes. Theoretical analysis is performed to identify the root causes of the observed performance enhancement, providing valuable insight into the underlying physics of contact engineering and its impact on OFET performance. In addition, the thesis explores the impact of dynamic trapping on highfrequency transistor performance and presents innovative methods for characterizing traps. Through the use of TCAD simulations, a comprehensive study of the internal quantities of organic transistors is conducted. The study provides a critical step towards developing a physics-based compact model for OFETs that can capture the essential physics of the device. Overall, this thesis provides comprehensive guidelines for reliable parameter extraction and performance improvement of OFETs. It makes significant contributions to the understanding of their underlying physics and lays the foundation for the development of physics-based compact models for OFETs, which could potentially revolutionize the field of organic electronics.

Organic electronics is a rapidly evolving field with vast number of applications having high potential for commercial success. Although a great progress has been made, many organic electronic applications: organic light-emitting diodes (OLEDs), organic fieldeffect transistors (OFETs), organic solar cells, etc; still require further optimization to fulfill the requirements for successful commercialization. For many applications, available at this time organic materials do not provide satisfactory performance and stability, which hinders the possibility of a large-scale production. Therefore, the key ingredient needed for a successful improvement in performance and stability of organic electronic devices is in-depth knowledge of physical and chemical properties of molecular and polymeric materials. Since many applications encompass several thin film layers made of organics, and often also inorganic materials, the understanding of both organic-organic and hybrid interfaces is yet another important issue necessary for the successful development of organic electronics. The research presented in this thesis is based mainly on photoelectron spectroscopy, which is an experimental technique especially suited to study both surfaces and interfaces of materials. In the thesis, the properties of one of the most successful polymeric materials, poly(3,4-ethylenedioxythiophene), often abbreviated as PEDOT, have been extensively studied. The research was done in close cooperation with an industrial partner – AGFA Gevaert, Belgium. The study was focused on the exploration of the intrinsic properties of the material, such as stability, morphology and conductivity. In addition, however, a possibility of alternation of these properties was also explored. This thesis reports also about investigations of the properties of various organic-organic and hybrid interfaces. The energy level alignment at such interfaces plays important role in charge injection and performance of the thin film organic-based devices. The conditions for different energy level alignment regimes at the various interfaces have been studied. The studies on interfaces were performed in close collaboration with the R&D division of DuPont Corporation, USA. This work led to the significant advances in understanding of the interface energetics and properties of industryrelevant organic materials, as represented not only by published scientific papers, but also patent applications.

The work carried out in this thesis systematically investigates the correlation between microstructures and electronic properties of organic semiconductors. The major directions that were pursued in this thesis are: (i) studies on structure-property relationship by rational design and synthesis of monodisperse oligomers with varying chain-lengths (ii) role of electronic properties and aggregation (microstructures) in governing singlet fission (SF). In the first part of the thesis, the optical, structural and charge transport properties of Diketopyrrolopyrrole (DPP)-based oligomers, as a function of the chain length, has been discussed. The energy bands became wider with an increase in chain length and a gain in backbone electron affinity was observed, with an offset in microstructural order. With an increase in chain length, the tendency to form intramolecular aggregates increased as compared to intermolecular aggregates due to the onset of backbone conformational defects and chain folding. An insight into the solid-state packing and microstructural order has been obtained by steady-state and transient spectroscopy, grazing incidence small angle x-ray scattering (GISAXS), atomic force microscopy (AFM) and transmission electron microscopy (TEM) studies. The charge-carrier mobilities varied in accordance with the degree of microstructural order as: dimer > trimer > pentamer. A library of DPP-DPP based trimers was also generated by modifying the donor chromophore (phenyl, thiophene and selenophene) in the oligomer backbone. Highest n-channel mobility of ~0.2 cm2V-1s-1 was obtained which validated that: (a) the effect of solid-state packing predominates the effect of backbone electronic structure on charge carrier mobility. Although oligomers possess lesser backbone defects than polymers in general, their charge carrier mobilities were not comparable to that of 2DPP-OD-TEG polymer, which forms highly oriented and isotropic edge-on crystallites/microstructures in the thin film, shows high n-channel mobility of 3 cm2V-1s-1 and band-like transport ;(b) although delocalized electronic states are achieved at greater chain lengths, the degree of solid-state microstructural order drastically reduces which leads to lower charge carrier mobilities; (c) conformational collapse resulted in lower electron mobilities and an increase in ambipolarity. The later part of the thesis debates on the relative contribution of electronic structure and aggregation (microstructures) in governing singlet fission (SF). Motivated by the recent SF model in carotenoid aggregates, a DPP-DPP based oligomer was synthesized by incorporating a vinylene bridge to imbue “polyene” character in the chromophore. Transient Spectroscopy (TA) measurements were carried out to monitor the formation of triplet states in the oligomer and to probe the occurrence of singlet fission. Although the oligomer exhibits “polyene” character like a typical “carotenoid aggregate”, it did not show singlet fission because of the additional stabilization of the singlet (S1) state which reduces the ∆EST. This study rationalized the importance of judicious control of band structures as well as microstructures to observe the SF phenomenon in this category of chromophores. The novel synthetic protocol provides the scope to tailor DPP-DPP based materials with desired effective conjugation lengths and side chains and can foreshow great prospects for future generation of organic electronics.

Organic semiconducting polymers are widely employed in organic electronics such as organic photovoltaics (OPVs), organic field-effect transistors (OFETs) and organic light emitting diodes (OLEDs). Their remarkable mechanical and charge transport properties as well as solution processability allow low-cost fabrication of light-weight and flexible devices. Among them indacenodithiophene (IDT)-based materials are promising candidates for application in organic electronics. Due to their low energetic disorder, extended conjugation and high electron density the IDT-based polymers show high field-effect mobilities and high absorption coefficients. However, their synthesis suffers from long reaction sequences and is often accomplished using toxic materials. Commercialization requires development of more efficient and sustainable reaction pathways to ease tailoring of structures and to limit molecular defects. Herein, the development of new synthetic pathways towards IDT-based polymers is presented in which all C-C coupling steps are achieved by C-H activation – an atom-economic alternative to conventional transition-metal catalyzed cross couplings. Two different strategies were established to synthesize a series of well-defined IDT-based homo- and copolymers with different side chain patterns and varied molecular weights. The first way starts by synthesis of a precursor polymer and subsequent cyclization affording IDT homopolymers. In the second approach, cyclized IDT monomers were prepared first and then polymerized using direct arylation polycondensation (DAP) yielding IDT homo- and copolymers. The synthetic pathways were optimized in terms of maximizing molecular weights and limiting defect structures. While the first pathway enables synthesis of well-defined homopolymers, the latter is the method of choice for preparation of IDT-based copolymers in high yields and adjustable molecular weights. The polymers were further characterized in detail by optical, thermal, electrical and morphological analyses. OFETs as well as all-polymer solar cells (all-PSCs) were fabricated to investigate the influence of structural modifications and molecular weight on their optoelectronic performance. Thus, this thesis provides a comprehensive study of the structure-property correlations of IDT-based polymers and simplified synthetic protocols for the design and preparation of donor-acceptor copolymers in the future.