Date of Award

2020

Document Type

Dissertation

Degree Name

Doctor of Philosophy (PhD)

Department

Materials Science

First Advisor

Madalina I. Furis

Second Advisor

Matthias . Brewer

Abstract

Quantum coherence plays a vital role in the excitonic properties of organic semiconductors. Several theoretical and experimental studies have shown an unprecedented role of coherence in charge transfer and transport processes, which in turn can improve the performance of electronic devices. Specifically, an enhancement of exciton coherence size can result in fast energy transport and efficient charge separation. The ability to tailor the design and performance of organic electronics based on exciton coherence effects represents the possibility of ultrafast electronic applications in communication and information technology.

The objective of this thesis is the excitonic coherence studies of 1D crystalline thin films of phthalocyanine-based organic semiconductors using steady-state and time-resolved photoluminescence spectroscopy (TRPL). One of the main focuses of this work is on investigating the correlation of intermolecular interactions, $\pi$ orbital overlap and dynamic disorders on the excitonic coherent behaviors in crystalline thin films of various phthalocyanine derivatives (i.e. H$_2$TPP, H$_2$OBPc, H$_2$OCPc, and H$_2$OBNc). Specifically, coherence lengths, exciton-phonon coupling strengths and the nearest neighbor (NN) interaction strengths are determined via: (1) the PL ratio of the excitonic coherence transition and its first vibrational replica and (2) the temperature evolution of radiative recombination lifetimes of coherent excitons. This study showed that the optimum coherence size and the robustness of excitonic coherence can be achieved by a complex interplay between NN interaction, vibrational energies and the coupling to vibrational modes. In particular, it is shown that the shortest NN distance does not ensure the achievement of maximum coherence length within the four investigated phthalocyanine species. Instead, the largest coherence length is measured in the octabutoxy derivative, where the saddle shape of the molecule and crystalline packing results in weaker coupling to the acoustic phonons modes despite having larger intermolecular NN distance. In addition, the effect of static and dynamic disorders on the behavior of exciton coherence is explored by alloying two phthalocyanine derivatives that are close in band gap energies and possess large coherence lengths, H$_2$OBPc and H$_2$OBNc. This study demonstrated the successful tuning of exciton coherence lengths and excitonic parameters in organic analogues of semiconductor alloys, H$_2$OBNc$_x$H$_2$OBPc$_{1-x}$. Furthermore, the correlation of exciton-phonon coupling and radiative recombination rate of coherent excitons with increasing alloy concentration or static disorders are successfully revealed.

Language

en

Number of Pages

160 p.

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