Photo-physical Characterization of Donor-Acceptor Systems using Ultrafast Laser Spectroscopy

Abstract

In donor-acceptor systems, ultrafast interfacial charge transfer (CT), charge separation (CS) and charge recombination (CR), are among the key factors in determining the overall efficiency of the optoelectronic devices. In this regime, precise knowledge of the mechanisms of these processes on the femtosecond scale is urgently required. In this dissertation, using femtosecond transient absorption and mid-Infrared spectroscopies along with steady-state absorption and emission measurements, we are not only able to address the fundamental understanding of these ultrafast dynamical processes, but also control them at various inter- and intramolecular electron donor-electron acceptor systems. In the photoinduced intermolecular charge transfer systems, where donor and acceptor are separated from each other, three systems have been investigated; cationic poly[(9,9-di(3,3′-N,N′-trimethylammonium) propyl fluorenyl-2,7-diyl)-alt-co-(9,9-dioctyl-fluorenyl-2,7-diyl)] diiodide salt (PFN) conjugated polymer donor with 1,4-dicyanobenzene (DCB) acceptor, negatively charged porphyrin (POS) donor with positively charged (PFN) acceptor, and finally, positively charged (PFN) donor with negatively charged graphene carboxylate (GC) acceptor. Based on studying these three systems, we were able to explore some important factors and deriving forces including chemical structure, electrostatic interactions, energy band alignment, hydrogen bonding and solvents with different polarities and capabilities for hydrogen bonding

that influence the rate and efficiency of the charge transfer at the interfaces of these donor-acceptor systems. For instance, unlike the conventional understanding of the key role of hydrogen bonding in promoting the charge-transfer process, our results reveal that the hydrogen-bonding increases the spacing between the donor and acceptor units which significantly hinders the charge-transfer process. On the other hand, in the photoinduced intramolecular charge transfer systems, where donor and acceptor are chemically attached to each other, we investigate the effects of conjugation length on photoinduced charge transfer in π-conjugated oligomers naphthalene diimide (NDI) end-capped oligo(phenylene ethynylene)s (PEn-NDI), and poly-(phenylene ethynylene) (PPE) donor backbone with (NDI) acceptor end-caps (PPE-NDI-n) systems. The results of femtosecond transient absorption and mid-IR spectroscopies show that the charge separation occurs on the 1-10 ps time scale with the rates decreasing as oligomer length increases in PEn-NDI system. In addition, in PPE-NDI-n system, the fluorescence quenching measurements indicate very efficient photoinduced electron transfer from the PPE backbone to the NDI end-groups, and the transfer efficiency increases with decreasing the number of units. Finally, the new physical insights reported in this thesis provide an understanding of several key variable components involved, thus paving the way toward the exploitation of efficient charge transfer at donor-acceptor interfaces, which is the key element and urgently required for optimal optoelectronic-device performance.