Contorted Organic Semiconductors for Molecular Electronics

This thesis focuses on the synthesis, properties and applications of two types of contorted organic molecules: contorted molecular ribbons and conjugated corrals. We utilized the power of reaction chemistry to writing information into conjugated molecules with contorted structures and studied “structure-property” relationships. The unique properties of the molecules were expressed in electronic and optoelectronic devices such as field-effect transistors, solar cells, photodetectors, etc. In Chapter 2, I describe the design and synthesis of a new graphene ribbon architecture that consists of perylenediimide (PDI) subunits fused together by ethylene bridges. We created a prototype series of oligomers consisting of the dimer, trimer, and tetramer. The steric congestion at the fusion point between the PDI units creates helical junctions, and longer oligomers form helical ribbons. Thin films of these oligomers form the active layer in n-type field effect transistors. UV−vis spectroscopy reveals the emergence of an intense long-wavelength transition in the tetramer. From DFT calculations, we find that the HOMO−2 to LUMO transition is isoenergetic with the HOMO to LUMO transition in the tetramer. We probe these transitions directly using femtosecond transient absorption spectroscopy. The HOMO−2 to LUMO transition electronically connects the PDI subunits with the ethylene bridges, and its energy depends on the length of the oligomer. In Chapter 3, I describe an efficiency of 6.1% for a solution processed non-fullerene solar cell using a helical PDI dimer as the electron acceptor. Femtosecond transient absorption spectroscopy revealed both electron and hole transfer processes at the donor−acceptor interfaces, indicating that charge carriers are created from photogenerated excitons in both the electron donor and acceptor phases. Light-intensity-dependent current−voltage measurements suggested different recombination rates under short-circuit and open-circuit conditions. In Chapter 4, I discuss helical molecular semiconductors as electron acceptors that are on par with fullerene derivatives in efficient solar cells. We achieved an 8.3% power conversion efficiency in a solar cell, which is a record high for non-fullerene bulk heterojunctions. Femtosecond transient absorption spectroscopy revealed both electron and hole transfer processes at the donor-acceptor interfaces. Atomic force microscopy reveals a mesh-like network of acceptors with pores that are tens of nanometers in diameter for efficient exciton separation and charge transport. This study describes a new motif for designing highly efficient acceptors for organic solar cells. In Chapter 5, I compare analogous cyclic and acyclic π-conjugated molecules as n-type electronic materials and find that the cyclic molecules have numerous benefits in organic photovoltaics. We designed two conjugated cycles for this study. Each comprises four subunits; one combines four electron-accepting, redox-active, diphenyl-perylenediimide subunits, and the other alternates two electron-donating bithiophene units with two diphenyl-perylenediimide units. We compare the macrocycles to acyclic versions of these molecules and find that, relative to the acyclic analogs, the conjugated macrocycles have bathochromically shifted UV-vis absorbances and are more easily reduced. In blended films, macrocycle-based devices show higher electron mobility and good morphology. All of these factors contribute to the more than doubling of the power conversion efficiency observed in organic photovoltaic devices with these macrocycles as the n-type, electron transporting material. This study highlights the importance of geometric design in creating new molecular semiconductors. In Chapter 6, I describe a new molecular design that enables high performance organic photodetectors. We use a rigid, conjugated macrocycle as the electron acceptor in devices to obtain high photocurrent and low dark current. We directly compare the macrocyclic acceptor devices to an acyclic control device; we find that the superior performance of the macrocycle originates from its rigid, conjugated, and cyclic structure. The macrocycle’s rigid structure reduces the number of charged defects originating from deformed sp2 carbons and covalent defects from photo/thermo-activation. With this molecular design we are able to suppress dark current density while retaining high responsivity in an ultra-sensitive non-fullerene organic photodetector. Importantly, we achieve a detectivity of ~10^14 Jones at near zero bias voltage. This is without the need for extra carrier blocking layers commonly employed in fullerene-based devices. Our devices are comparable to the best fullerene-based photodetectors, and the sensitivity at low working voltages (< 0.1 V) is a record for non-fullerene OPDs