The π-conjugated organic and polymeric semiconducting materials have attracted much attention in the past years due to their significant potential in applications to electronic and optoelectronic devices including organic field-effect transistors (OFETs), organic photovoltaics (OPVs), and organic light-emitting diodes (OLEDs), etc. Yet, organic and polymeric semiconductors still have challenges associated with their relatively low charge carrier (hole and electron) transport mobilities and ambient stability in OFET applications. This dissertation discusses the molecular engineering on backbones and side-chains of π-conjugated semiconducting polymers to enhance the hole and electron field-effect mobilities. Three donor-acceptor copolymers, the hole transport (p-type) poly(hexathiophene-co-benzo- thiazole) (PBT6), the hole transport poly(thiophenes-benzothiadiazole-thiophenes-diketopyrrolo- pyrrole) (pTBTD), and the electron transport (n-type) poly(dithieno-diketopyrrolopyrrole-bithiazole) (PDBTz) have been developed. Besides, the effect of polymer side chains on polymer solution-processability and charge carrier transport properties was systematically investigated: a side chain 5-decylheptadecyl having the branching position remote from the polymer backbone merges the advantages of the improved solubility from traditional branched side chains in which the branch chains are close to polymer backbone and the effective π-π intermolecular interactions commonly associated with linear side chains. This indicates the potential of side chain engineering to facilitate the charge carrier transport performance of organic and polymeric semiconductors. Additionally, PDBTz solution-processing to OFETs based on non-halogenated solvents (xylenes and tetralin) was studied. The resultant thin-film OFET devices based on non-halogenated solvents exhibited similar film morphology and field-effect electron mobilities as the counterparts based on halogenated solvents, indicative of the feasibility of developing high mobility OFET devices through more environmentally-benign processing.

Increasing global energy demands and diminishing supplies of conventional fuels are forcing the world to focus more on alternative power sources that are both renewable and ecologically benign. Solar energy is clean, regularly available and can be harvested without sacrificing valuable land space. Due to the associated cost of solar cells, however a very small portion of the world’s energy needs are supplied by the sun. Solution-processable organic photovoltaics (OPVs) offer the promise of lower production costs relative to conventional (silicon) solar cell technology. Solution-processing can be performed using reel-to-reel manufacturing, with printing and coating techniques that are significantly cheaper than current processing methods for inorganic semiconductors. Although OPV efficiency values currently remain inferior to those of conventional solar cells, the rate of improvement is much higher in OPVs than in other solar cell technologies. Recently an efficiency exceeding 10% was reported for organic solar cells. An important difference between organic and conventional solar cells is the charge carrier mobility of the semiconductors, which tends to be relatively low in organic semiconductors. Recent advances in molecular design have led to polymer semiconductor materials that possess hole mobility values similar to that of amorphous silicon. The present study investigates potential improvements in OPV devices that can be achieved through the application of high hole mobility polymer semiconductor donors. Two diketopyrrolopyrrole-based polymers, PDQT and PDBFBT, were selected for the role of electron donor in OPV devices due to their high mobilities and their optimum optical and electrical properties. Optimization of the process parameters was performed using PC61BM as the acceptor. A relatively high quantity of PC61BM (3 - 4 × the weight of the donor) is required in the donor-acceptor blends of both polymers in order to balance the high hole mobility. For these donor-acceptor blends, a solvent system consisting of chloroform/ortho-dichlorobenzene (4:1 v/v) is necessary for proper solubility, and an additive, 1,8-diiodooctane, is required to achieve an acceptable morphology. The main benefit expected from the use of high mobility semiconductors is reduced charge recombination. This was studied in relation to the active layer thickness in standard and inverted OPV devices prepared using PC61BM as the acceptor. Normally the thickness of the active layer is required to be low (~100 nm) due to the poor charge transport mobility of the carriers. In this study, rather consistent power conversion efficiencies were achieved throughout a wide range of active layer thicknesses (~100 nm to ~800 nm). A comparison between standard and inverted device configurations demonstrates that the inverted configuration is more suitable for achieving thicker active layers when a high hole mobility donor is used. This is attributed to the longer hole collection path in the inverted structure, which can benefit from using a high hole mobility material. Increasing the absorption spectra of the donor-acceptor blend was studied by substituting PC71BM for PC61BM. The improved absorption leads to greater charge generation. In PDQT devices, the increase in absorption that is contributed by PC71BM appears to be of greatest benefit when active layers are not very thick. Therefore, when thick active layers (>500 nm) are required, the use of PC61BM is sufficient, in conjunction with a high mobility donor. Finally, an increase in a polymer’s crystallinity can often lead to greater mobility. This can be accomplished through various annealing techniques. The improved crystallinity of PDBFBT that occurs as a result of thermal annealing was studied in OPV applications. Although hole mobility of PDBFBT in the lateral direction improves with thermal annealing, mobility in the vertical direction decreases with increasing temperature. This suggests that the crystallinity of PDBFBT is oriented in the lateral direction as opposed to the vertical direction, thereby directing charge flow horizontal to the surface. With thermal annealing, an optimal amount of PC61BM added to PDBFBT can increase the vertical mobility to fairly high values. Nevertheless, the efficiency of standard and inverted OPV devices decreases with increased annealing temperature. This is attributed to agglomeration of PC61BM that occurs from an increase in annealing temperature. The results of this study demonstrate that thermal annealing is not beneficial for PDBFBT:PC61BM films in OPV applications due to the vertical orientation of devices. All of the studies presented in this work involve the use of high hole mobility polymer semiconductors as donor materials for OPV applications. This work will provide a deeper understanding of the properties required for the development of new semiconductor materials in OPV applications. Furthermore, this work will be very useful for the design of device structures for more feasible manufacturing of large area OPV devices via high speed roll-to-roll printing processes.

Increasing global energy demands and diminishing supplies of conventional fuels are forcing the world to focus more on alternative power sources that are both renewable and ecologically benign. Solar energy is clean, regularly available and can be harvested without sacrificing valuable land space. Due to the associated cost of solar cells, however a very small portion of the world’s energy needs are supplied by the sun. Solution-processable organic photovoltaics (OPVs) offer the promise of lower production costs relative to conventional (silicon) solar cell technology. Solution-processing can be performed using reel-to-reel manufacturing, with printing and coating techniques that are significantly cheaper than current processing methods for inorganic semiconductors. Although OPV efficiency values currently remain inferior to those of conventional solar cells, the rate of improvement is much higher in OPVs than in other solar cell technologies. Recently an efficiency exceeding 10% was reported for organic solar cells. An important difference between organic and conventional solar cells is the charge carrier mobility of the semiconductors, which tends to be relatively low in organic semiconductors. Recent advances in molecular design have led to polymer semiconductor materials that possess hole mobility values similar to that of amorphous silicon. The present study investigates potential improvements in OPV devices that can be achieved through the application of high hole mobility polymer semiconductor donors. Two diketopyrrolopyrrole-based polymers, PDQT and PDBFBT, were selected for the role of electron donor in OPV devices due to their high mobilities and their optimum optical and electrical properties. Optimization of the process parameters was performed using PC61BM as the acceptor. A relatively high quantity of PC61BM (3 - 4 × the weight of the donor) is required in the donor-acceptor blends of both polymers in order to balance the high hole mobility. For these donor-acceptor blends, a solvent system consisting of chloroform/ortho-dichlorobenzene (4:1 v/v) is necessary for proper solubility, and an additive, 1,8-diiodooctane, is required to achieve an acceptable morphology. The main benefit expected from the use of high mobility semiconductors is reduced charge recombination. This was studied in relation to the active layer thickness in standard and inverted OPV devices prepared using PC61BM as the acceptor. Normally the thickness of the active layer is required to be low (~100 nm) due to the poor charge transport mobility of the carriers. In this study, rather consistent power conversion efficiencies were achieved throughout a wide range of active layer thicknesses (~100 nm to ~800 nm). A comparison between standard and inverted device configurations demonstrates that the inverted configuration is more suitable for achieving thicker active layers when a high hole mobility donor is used. This is attributed to the longer hole collection path in the inverted structure, which can benefit from using a high hole mobility material. Increasing the absorption spectra of the donor-acceptor blend was studied by substituting PC71BM for PC61BM. The improved absorption leads to greater charge generation. In PDQT devices, the increase in absorption that is contributed by PC71BM appears to be of greatest benefit when active layers are not very thick. Therefore, when thick active layers (>500 nm) are required, the use of PC61BM is sufficient, in conjunction with a high mobility donor. Finally, an increase in a polymer’s crystallinity can often lead to greater mobility. This can be accomplished through various annealing techniques. The improved crystallinity of PDBFBT that occurs as a result of thermal annealing was studied in OPV applications. Although hole mobility of PDBFBT in the lateral direction improves with thermal annealing, mobility in the vertical direction decreases with increasing temperature. This suggests that the crystallinity of PDBFBT is oriented in the lateral direction as opposed to the vertical direction, thereby directing charge flow horizontal to the surface. With thermal annealing, an optimal amount of PC61BM added to PDBFBT can increase the vertical mobility to fairly high values. Nevertheless, the efficiency of standard and inverted OPV devices decreases with increased annealing temperature. This is attributed to agglomeration of PC61BM that occurs from an increase in annealing temperature. The results of this study demonstrate that thermal annealing is not beneficial for PDBFBT:PC61BM films in OPV applications due to the vertical orientation of devices. All of the studies presented in this work involve the use of high hole mobility polymer semiconductors as donor materials for OPV applications. This work will provide a deeper understanding of the properties required for the development of new semiconductor materials in OPV applications. Furthermore, this work will be very useful for the design of device structures for more feasible manufacturing of large area OPV devices via high speed roll-to-roll printing processes.

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%).

Les cellules solaires organiques (OSC) apparaissent comme une technologie prometteuse pour les énergies renouvelables en raison de leur poids léger, leur grande flexibilité et leur processus de fabrication peu coûteux. Jusqu'à présent, la plupart des OPV ont utilisé des dérivés de Fullerene, tels que PCBM ou PC71BM, en tant qu'accepteur d'électrons dans la couche active, qui s'est avéré être un goulet d'étranglement pour cette technologie. Par conséquent, le développement d'accepteurs non-fullerene est devenu la nouvelle force motrice de ce domaine. Les cellules solaires tout-polymères (tous-PSC) qui ont les avantages de la robustesse, de la stabilité et de l'accessibilité ont déjà atteint PCE jusqu'à 9%. Ainsi, le développement de nouveaux matériaux accepteurs est impératif pour améliorer les performances de tous les PSC. / Organic solar cells (OSCs) appear as a promising technology for renewable energy owing to their light weight, great flexibility and low-cost fabrication process. So far most of the OPV shave been using fullerene derivatives, such as PCBM or PC71BM, as the electron acceptor in the active layer, which have been proven to a bottleneck for this technology. Therefore,developing non-fullerene acceptors has become the new driving force for this field. All-polymer solar cells (all-PSCs) that have the advantages of robustness, stability and tunability have already achieved PCE up to 9%. Thus, developing novel acceptor materials is imperative for improving the performance of all-PSCs.

Development of efficient and clean energy sources to meet the ever-increasing de- mand of humankind is one of the greatest challenges of the 21st century. There is a dire need to decarbonise the power sector, and the focus needs to shift to re- newable resources such as wind and solar energy. In this regard, organic solar cells are a promising and novel technology owing to its low carbon footprint, innovative applications, and possible integration into the current infrastructure. Due to its unique advantages, a considerable research effort has been put into its development in the last decades. As a result, the power conversion efficiency (PCE) of the organic photovoltaics has steadily risen from as low as 0.5% to around 17 % at the current stage. This improvement primarily originates from the better understanding of the underlying physical processes and as a result of extensive material development. In the most general case, organic solar cells consist of a binary blend of an electron donating and an electron accepting organic semiconductor forming the so-called ‘bulk-heterojunction’ (BHJ) morphology. Thermodynamics places an upper limit on the power conversion efficiency (PCE) of binary blend BHJ devices and for further enhancement in efficiency novel device concepts like the use of ternary blends and tandem device architectures is being investigated. In relation to these approaches, the development of low optical-gap (Eopt ≤ 1.5 eV) organic semiconductors has gained importance as these materials provide for the complementary absorption with respect to the other components and better harvesting of the solar spectrum. This work mainly deals with the investigation of low optical gap donor and acceptor materials for organic solar cells. We investigate the effect of the molecular structure on the device performance and the photophysical processes in the binary and ternary blend configuration. In the first part of the thesis, we study a family of low optical- gap diketopyrrolopyrrole (DPP) based polymers while varying the conjugated core and the branching position and length of the solubilizing alkyl side chains. The branching position of the side chains is found to have a significant influence on the polymers ability to crystallize, which in turn influences the mobility of free charge carriers. The branching position also affects the solubility of the polymer, which in turn influences the morphology of the bulk-heterojunction (BHJ) and ultimately the yield of photogenerated charge carriers. To investigate the electron transfer and charge separation dynamics in the blends consisting of DPP polymers and fullerene, we employed ultrafast pump-probe spec- troscopic techniques. In the spectroscopy data, we observe signatures suggesting an ultrafast electron transfer process and an efficient charge separation process due to the high mobility of the free charge carriers shortly after separation (∼10-100 ps). Lastly, we investigated indacenodithiophene (IDT) based non-fullerene acceptor (NFA) molecules. In particular, we studied the effect of fluorination on the device performance when these acceptors are blended with PTB7-Th and P3HT donor polymers. The kinetics of the photophysical processes in the binary and ternary blends are characterized using ultrafast spectroscopy and related to the morphology of the blend and the molecular structure of the acceptors. Overall, we investigated the structural variations in the DPP polymers and flu- orinated non-fullerene acceptor (NFA) molecules and suggest design rules for the synthesis of optimal DPP polymers and non-fullerene acceptors to achieve supe- rior device performance. Additionally, we also shed light on the phenomenological processes happening on an ultrafast time scale (0.2-1000 ps) in the binary and the ternary blends with the aim of developing a better understanding of the photophys- ical processes in these promising material systems.

During past years, organic-based electronic devices revealed high promise to supplement the ubiquitous silicon-based electronic devices and enable new fields of applications. At the center of this development is the considerable progress regarding π-conjugated polymer semiconductors (PSCs): Due to their processability from solution, light-weight, as well as low-cost, PSCs are now evolving towards production-scale of new technologies, e.g., in organic solar cells (OSCs), organic field-effect transistors (OFETs), and organic light emitting diodes (OLEDs). Especially OFETs are of fundamental importance, as they constitute the switching units in all logic circuits and display technologies. However, the future world is expected to be full with smart electronics and communication devices integrated in clothes, tools and even interacting with the human body, e.g., as on-skin wearable sensors. For this the electrically-active material, just as a human tissue, requires to combine several properties in addition to being charge conducting: They need to show (i) mechanical softness, (ii) capacity to repair, (iii) multimodal sensitivity, as well as (iv) biodegradability. Here, PSCs still face challenges as they are brittle and break upon applying a mechanical stress. When trying to address this issue, the existing knowledge on mechanical properties of well-established polymeric plastics, e.g., polystyrene, cannot be directly applied for several reasons, e.g., (i) the bulkiness of monomers (including long side-chains), (ii) the rigid π-conjugated backbone, (iii) the low degree of polymerization, (iv) the small quantities in which PSCs are available, etc. Moreover, these kinds of materials should not only be mechanically compliant and stretchable, but furthermore retain their charge mobility upon stretching, and withstand numerous of mechanical stretching cycles. Considering this complex problem, researchers have been developing and investigating several approaches to combine good electrical properties and mechanical compliance within one material. These approaches include (i) stress-accommodating engineering, (ii) blending of PSCs into elastic matrix, as well as (iii) molecular engineering approach. The latter seeks to interlink mechanical and electrical properties on the molecular level, i.e., synthesize polymers that are charge conducting and stretchable. Different strategies were tested, from the modification of side chains, to the introduction of conjugation breakings spacers into the backbone. Selected works sought to incorporate stretchability and conductivity by utilizing block copolymers, i.e., covalently linking a conjugated and a non-conjugated polymer chain, resulting in a phase separation of both constituents and preserving their respective properties. The ultimate goal of this work is to achieve an intrinsically stretchable and electrically high-performing PSC via the block copolymer approach. This is done by connecting organosilicone, namely the polydimethylsiloxane (PDMS) elastomer – possessing outstanding mechanical properties, as well as good environmental and air stability – with a conjugated diketopyrrolopyrrole (DPP)-based donor-acceptor copolymer. The final obtained structure of this polymer is a tri-block copolymer (TBC) consisting of an inner DPP-based polymer block and two outer soft PDMS polymer blocks. The content of PDMS block can be controlled and be very high (up to 67 wt%), and easy processing, e.g., via shear coating, is possible. Relatively high charge carrier mobilities – in the same range as the reference DPP-based copolymer (i.e., without outer PDMS blocks) – are retained, and the block copolymers withstands numerous stretching cycles (up to 1500 cycles) without losing electrical functionality. Finally, one of the block copolymers was successfully incorporated into a biosensor for COVID-19 antibodies and antigens detection. Overall, the findings of this work show that the block copolymer is a highly versatile approach to obtain functional and stretchable semiconductors with high charge carrier mobilities. Block copolymers consisting of a high-performing donor-acceptor PSC and a biocompatible elastomer could contribute towards one of the long-term goals of organic electronics – the realization of mechanically compliant materials for applications in stretchable electronics (e.g., wearable sensors, electronic skin, etc.).

The present thesis is focused on the rational design of Diketopyrrolopyrrole based π- conjugated polymers for organic electronics. The thesis is organized into six different chapters and a brief description of the individual chapters is provided below. Chapter 1 briefly describes the physics governing the electronic processes occurring in organic photovoltaics (OPVs) and organic field-effect transistors (OFETs) followed by design rules for the synthesis of conjugated polymers for organic electronics. Diketopyrrolopyrrole (DPP) based π-conjugated materials and their development in OPVs and OFETs have been highlighted. Chapter 2 discusses the synthesis and characterization of a series of small molecules of DPP derivatives attached with different alkyl chains. Influence of side chains on the photophysical properties of these DPP derivatives have been studied by UV-visible spectroscopy and DFT calculations. Crystal structure studies revealed the effect of alkyl chains on the torsional angle, crystal packing, and intermolecular interactions such as π-π stacking. Chapter 3 reports the synthesis of novel diketopyrrolopyrrole-diketopyrrolopyrrole (DPPDPP) based conjugated copolymers and their application in high mobility organic field-effect transistors. Effect of insulating alkyl chains on polymer thin film morphology, lamellar packing and π-π stacking interactions have been studied in detail. Investigation of OFET performance of these DPP-DPP copolymers with branched alkyl chains (N-CS2DPP-ODEH) resulted in low charge carrier mobilities as compared to the polymers (N-CS2DPP-ODHE) with linear alkyl chains. Polymer with triethylene glycol side chains (N-CS2DPP-ODTEG) exhibited a high field-effect electron mobility value of ~3 cm2V-1s-1 with a very low threshold voltage of ~2 V. Chapter 4 investigates the effect of torsional angle on the intermolecular interactions and charge transport properties of diketopyrrolopyrrole (DPP) based polymers (PPDPP-OD-HE and PPDPP-OD-TEG). Grazing incidence x-ray diffraction studies shows the different orientation of the polymer crystallites and lamellar packing involved in polymer thin films. Investigation of OFETs evidenced the effect of torsional angle on the charge transport properties where the polymer with higher torsional angle PPDPP-OD-TEG resulted in high threshold voltage with less charge carrier mobility compared to the polymer with lower torsional angle (N-CS2DPP-OD-TEG). Chapter 5 investigates the effect of photoactive material morphology on the solar cell device performance, and charge transfer kinetics by adding high boiling point processing additives. DPP based donor-acceptor (D-A) type low band gap polymers (PTDPPQ and PPDPPQ) have been synthesized and employed in bulk-heterojunction (BHJ) solar cells with the acceptor PC71BM. Addition of processing additive 1,8-diiodooctane (DIO) resulted in three order improvements in power conversion efficiency (PCE). Chapter 6 describes the design and synthesis of two diketopyrrolopyrrole based copolymers (PPDPP-BBT and PTDPP-BBT) for their application in organic devices such as field-effect transistors and bulk-heterojunction solar cells. Investigation of OFET performance of these DPP based copolymers displayed hole mobilities in the order of 10-3 cm2V-1s-1. The semiconductor-dielectric interface has been characterized by capacitance-voltage, and Raman scattering methods. In summary, the work presented in this thesis describes the synthesis and characterization of diketopyrrolopyrrole based new polymeric semiconductors. Effects of insulating side chains and torsional angle on the charge transport properties of these polymers in OFETs have been investigated. This work also describes the effect of solvent additives on the active layer morphology and BHJ solar cell device performance. The results described here show that these materials have potential application as active components in plastic electronics.