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.

The present thesis is focused on rational design and synthesis of π-conjugated donor-acceptor (D-A) type oligomers and polymers. It is organized in six different chapters and a brief discussion on the content of the individual chapter is provided below. Chapter 1 briefly describes the charge transport properties of organic semiconductors followed by recent development of different organic semiconducting materials mainly for applications in OFET and solar cells have been highlighted. Chapter 2 explores the synthesis and characterization of two new liquid crystalline, D-A type bithiophene-benzothiazole derivatives. The liquid crystalline properties of the materials have been studied in detail with optical polarizing microscopic images and differential scanning calorimetry and found that these materials possess highly ordered smectic A liquid crystalline phase. Their charge transport properties have also been investigated by fabricating OFET devices. Chapter 3 describes the photophysical properties and OFET performance of quinoxaline based donors-acceptor-donor (D-A-D) type molecules. Depending on the flexibility and rigidity of the conjugated backbone these materials show liquid crystalline behaviour. Investigation of their OFET performance indicated that these molecules exhibit p-type mobility up to 9.7 x 10-4 cm2V-1s-1 and on/ off ratio of 104. Chapter 4 investigates excited state properties and OFET behavior of D-A-D type diketopyrrolopyrrole (DPP) derivatives end-capped with alkoxynaphthalene group. UV-Visible spectroscopy measurement shows strong intramolecular charge transfer (ICT) between donor and acceptor unit. Steady-state and time-resolved fluorescence measurements confirm the formation of excimer. The excited state interactions, the interchromophore separation and geometry of the molecules influence the extent of excimer formation. Finally, the OFET behavior of these DPP based materials has been studied using different dielectric layers. Chapter 5 discusses the synthesis, characterization and properties of two new thieno[3,2-b]thiophene-DPP based donor-acceptor (D-A) type low band gap polymers (PTTDPP-BDT and PTTDPP-BZT). Investigation of OFET performance indicated that polymers exhibited ambipolar behaviour with hole mobility upto 1.0 x 10-3 cm2/Vs and electron mobility upto 8 x 10-5 cm2/Vs. Using polymer PTTDPP-BDT with electron acceptor C70PCBM, power conversion efficiency (PCE) around 3.26% in bulk heterojunction solar cell has been achieved. Chapter 6 describes the approach to tailor the energy levels of conjugated polymers (PTDPP-IDT and PTTDPP-IDT) based on Indacenodithiophene (IDT) coupled with DPP moieties. We have studied the photovoltaic performance of these conjugated polymers by blending with PCBM and P3HT. The importance of these materials in polymer/polymer blend solar cell has been emphasized. The photovoltaic devices with polymer/polymer blend solar cell exhibit high open-circuit voltages (VOC) of ~ 0.8 V. In summary, the work presented in this thesis describes synthesis, characterization and photophysical properties of new organic semiconductors and their importance in optoelectronic devices. This work also describes a general design principle of nonfullerene organic solar cell. The results described here show that these materials have potential application as active components in plastic electronics.