Linear and nonlinear optical properties of organic semiconductors

The optical properties of highly conjugated organic semiconductors can reveal quite a bit about their underlying chemistry and physics. This dissertation considers four different systems and applies both experimental and theoretical optical tools to understand them. Using absorption, emission, NMR, and quantum mechanical calculations, I first show how a non-aromatic to aromatic transition drives a large spectroscopic change in 2-methyl-1,4-diphenyl-2H-benzo[g]isoquinolin-3-one (MDP-BIQ) in the presence of hydrogen-bond donating impurities, and how this change might be used as an acid-base sensor. Second, I study poly(2-methoxy-5-(2'-ethylhexyloxy)p-phenylenevinylene) (MEH-PPV), a conjugated semiconducting polymer used as the emissive layer in organic light emitting diodes (OLEDs). By modeling the electric field distributions in two different MEH-PPV thin film architectures and comparing them to experiment, I show how the natural diffusion of individual polymer chains into a silica mesopore matrix creates graded-index waveguides that dramatically lower amplified spontaneous emission (ASE) thresholds. In the third case, I show how ASE quenching in neat MEH-PPV films cannot be attributed to optical effects, but instead must be due to chemical doping at the interface. Finally, using second harmonic generation (SHG), 2D x-ray diffraction, and optical modeling, I show that the crystallinity of neat MEH-PPV films can be measured with SHG and that the source of the SHG is due to electric quadrupole polarization from the bulk of the film rather than the more common electric dipole polarization from the interface.