Chad Miller Thesis Defense 10/7/16

Thesis Defense

Richards G. (Chad) Miller III

Friday, October 7, 2016
3:00PM (334 JFB)

Title: Morphological Effects on Spin-Dependent Electronic Processes in Poly[9,9-Dioctylfluorenyl-2,7-Diyl] Thin Film Organic Light Emitting Diodes

We have studied the role of spin-dependent processes on conductivity in polyfluorene (PFO) thin films by conducting continuous wave (c.w.) electrically detected magnetic resonance (EDMR) spectroscopy at temperatures between 10 K and 293 K using microwave frequencies between about 100 MHz and 20 GHz as well as pulsed EDMR at X-band (10 GHz). Variable frequency EDMR allows us to establish the role of spin-orbit coupling in spin-dependent processes whereas pulsed EDMR allows for the observation of coherent spin motion effects. We used PFO for this study in order to allow for the investigation of the effects of microscopic morphological ordering since this material can adopt two distinct intrachain morphologies: an amorphous (glassy) phase, in which monomer units are twisted with respect to each other, and an ordered (β) phase, where all monomers lie within one plane. In thin films of organic light-emitting diodes (OLEDs) the appearance of a particular phase can be controlled by deposition parameters and solvent vapor annealing, and is verified by electroluminescence spectroscopy. Under bipolar charge carrier injection conditions we conducted multi-frequency c.w. EDMR, electrically detected Rabi spin-beat experiments, Hahn-echo and inversion-recovery measurements. Coherent echo spectroscopy reveals electrically detected electron spin-echo envelope modulation (ESEEM) due to the coupling of the carrier spins to nearby nuclei spins. Our results demonstrate that while conformational disorder can influence the observed EDMR signals, including the sign of the current changes on resonance as well as the magnitudes of local hyperfine fields and charge carrier spin-orbit interactions, it does not qualitatively affect the nature of spin-dependent transitions in this material. In both morphologies, we observe the presence of at least two different spin-dependent recombination processes. At 293 K and 10 K, polaron-pair recombination through weakly spin-spin coupled intermediate charge carrier pair states is dominant, while at low temperatures, additional signatures of spin-dependent charge transport through the interaction of polarons with triplet excitons are seen in the half-field resonance of a triplet spin-1 species. This additional contribution arises since triplet lifetimes are increased at lower temperatures. We tentatively conclude that spectral broadening induced by hyperfine coupling is slightly weaker in the more ordered β-phase than in the glassy-phase, since protons are more evenly spaced, whereas broadening effects due to spin-orbit coupling, which impacts the distribution of g-factors, appears to be somewhat more significant in the β-phase.

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