Date of Award

2015

Document Type

Dissertation

Degree Name

Doctor of Philosophy (PhD)

Department

Materials Science

First Advisor

Madalina I. Furis

Abstract

Small molecule organic semiconductors such as phthalocyanines and their derivatives represent a very interesting alternative to inorganic semiconductor materials for the development of flexible electronic devices such as organic thin field effect transistors, organic Light Emitting Diodes and photo-voltaic cells. Phthalocyanine molecules can easily accommodate a variety of metal atoms as well in the central core of the molecule, resulting in wide range of magnetic properties. Exploration of optical properties of organic crystalline semiconductors thin films is challenging due to sub-micron grain sizes and the presence of numerous structural defects, disorder and grain boundaries. However, this can be overcome by fabricating macroscopically ordered semiconductor films by solution processing. Presence of fewer grain boundaries and defects while modifying the pi orbital overlap by controlling the molecular stacking by forming macroscopic long range ordered grains, was essential in understanding the delocalization and diffusion length and its role in magnetic exchange mechanisms in this system.

The origins of magnetic exchange mechanism between delocalized ligand electrons and spins in organic semiconductors has been of key interest as it underlies many complex optical and transport properties and is investigated in this thesis. The interaction between magnetic ions in organic magnetic semiconductors is quite challenging to interpret due to competing exchange mechanisms present in crystalline thin films. Better understanding of these exchange mechanisms is essential for tuning of magnetic exchange interaction to suit the need of practical magnetic storage and spintronic devices. Optical techniques such as linear dichroism, magnetic circular dichroism and magneto-photoluminescence are used and provided key understanding about the relation between excitons, spin exchange mechanisms and collective magnetic behavior of delocalized electrons in organic semiconductors. An enhancement in the collective magnetization of the crystalline thin films with strong exchange coupling between the delocalized ligand electrons and d-electrons is observed. The electronic states responsible for magnetic exchange are identified utilizing magnetic field and temperature dependent studies. Furthermore, soluble organics allowed engineering of organic analogues to diluted magnetic semiconductors (DMS) by creation of metal/metal-free Pc alloys. Optical studies provided crucial information about delocalization and diffusion lengths in these systems allowing fine tuning of this delocalization length scale and metal-metal distance. The exploration of magnetic behavior in metal/metal-free Pc alloys opens an avenue for tuning magnetic properties through an exchange similar to Ruderman-Kittel-Kasuya Yosida (RKKY) type interaction in organic magnetic semiconductors.

Language

en

Number of Pages

247 p.