We have synthesized norbornene-functionalized side-chain monomers for potential use as hole transporting and electron transporting/hole blocking materials in organic light-emitting diodes. TPD-norbornenes were prepared. The monomers demonstrated similar electrochemical and absorbance spectra to the parent TPD small molecule. The similarity is promising for using the monomers in OLEDs because TPD is a known blue-emitter with relatively high hole mobility in amorphous thin films. 1,10-Phenanthroline small molecules and monomers were synthesized to explore their potential as hole blocking materials in multilayer devices. We had difficulty purifying the monomers; however, the small molecules were slightly easier to reduce than commonly used hole blocking materials 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline and 4,7-diphenyl-1,10-phenanthroline.

Dissertation (Ph. D.)--University of Akron, Dept. of Polymer Science, 2009. / "August, 2009." Title from electronic dissertation title page (viewed 9/23/2009) Advisor, Stephen Z. D. Cheng; Committee members, Alexei P. Sokolov, Gustavo A. Carri, Darrell H. Reneker, Weiping Zheng; Department Chair, Ali Dhinojwala; Dean of the College, Stephen Z. D. Cheng; Dean of the Graduate School, George R. Newkome. Includes bibliographical references.

Thesis (M. S.)--Electrical and Computer Engineering, Georgia Institute of Technology, 2009. / Committee Chair: Gregory Durgin; Committee Member: Andrew Peterson; Committee Member: Bernard Kippelen.

Thesis (Ph.D)--Mechanical Engineering, Georgia Institute of Technology, 2010. / Committee Chair: Samuel Graham; Committee Member: Bernard Kippelen; Committee Member: David McDowell; Committee Member: Sankar Nair; Committee Member: Suresh Sitaraman. Part of the SMARTech Electronic Thesis and Dissertation Collection.

Thesis (Ph. D.)--University of Texas at Austin, 2005. / Vita. Includes bibliographical references.

Thesis (Ph. D.)--University of Texas at Austin, 2007. / Vita. Includes bibliographical references.

>Magister Scientiae - MSc / Applications of electrochemiluminescent conjugated polymers offer promising solutions in addressing the problem of light emitting devices. However, the challenging problems that hamper their application in light emitting devices are loss of signal due to diffusion of the electrochemiluminescence (ECL) reagent out of the detection zone, limited ability to repeatedly cycle an individual luminophore and high reagent consumption. In this work, the main objective was to produce conducting polymers with enhanced electrochemiluminescence by tuning the properties of the polymer itself. The electrochemical and photophysical properties of films of polyaniline (PANI) and poly(8-anilino-1- naphthalene sulfonic acids) (PANSA) synthesized through electro- and chemical polymerization methods were also investigated. The electrosynthesis of PANSA undoped and doped with anthracene sulfonic acid (ASA), 1,2-naphthaquinone-4-sulfonic acid (NSA) and carbon nanotubes (CNT) in acid medium was investigated and the cyclic voltammograms (CV) showed the growth of the polymer during polymerization. The CV multiscan characterization displayed that the growth of the polymer was dependent of the scan rate and the three redox couples were observed as indicative of the three redox states of typical polyaniline and its derivatives. The results also showed that the peak currents were diffusion controlled and the electron charge transport coefficient (De) of the electrosynthesized polymers was found to range between 10⁻⁸ and 10⁻⁹ cm² s⁻¹ for PANSA, PANSA-ASA, PANSA-NSA and PANSA-CNT. The De value indicates that the movement of electrons along the polymer chain was averagely fast. The transmission electron microscopy (TEM) was used to investigate the electronic morphology of the polymers and the TEM images showed an intertwinement of tubings which aggregate into a ring with a mixture of tubings and plastic sheets. The chemical synthesis of PANI, PANSA and PANI-NSA was carried out by using monomers analine, 8-anilino-1-naphthalene sulfonic acid, and aniline with 1,2- naphthaquinone-4-sulfonic acid, respectively, using oxidants. All chemically synthesized polymers exhibited quinoid and benzoid bands typically see in polyaniline FTIR and Raman spectra confirmed the successfully formation of polymers. The CV characterization of these polymers showed distinctive redox peaks. This proved that the polymers were electroactive, conductive and exhibited reversible electrochemistry. The De of the electrosynthesized polymers was found to be ~10⁻⁵ cm² s⁻¹ for chemically synthesized polymers. The electric conductivity measurement showed to increase from 10⁻⁴ to 10⁻² when aniline was polymerized with NSA dopant, this might be related to the process of electron transfer from dopant to polymer. Scanning electron microscopy for external morphology showed that the polymers were made of different nano- rods polymeric structures. Photophysical properties of electro- and chemically synthesized PANSA and PANI were investigated through UV-vis absorption, fluorescence behaviour, and lifetime. The UV-vis absorption spectra of these polymers showed that they exhibited absorption bands corresponding to the polyemeraldine redox state of typical polyaniline. The effect of dopants resulted in the increase in solubility of the polymers with a small shift of absorption bands due to incorporation of dopants in to the backbone of the polymer. The fluorescence emission spectra of the electrochemically synthesized PANSA with and without dopants were observed to be similar and mirror image of the excitation spectra and corresponding to the electronic band of the benzoid ring in the polyemeraldine form confirming that the fluorescing molecule in these polymers were the benzoid rings. However, the emission spectra of the chemically synthesized PANSA and PANI were different to excitation spectra due to loss of symmetry upon excitation. The effects of chemically synthesized PANI, PANSA and PANI-NSA addition on the photophysical properties of [Ru(bpy)₂(picCOOH)]²⁺.(ClO₄⁻)₂) were investigated in order to understand the interaction of polymer and [Ru(bpy)₂(picCOOH)]²⁺.(ClO₄⁻)₂. The analysis revealed that the presence of polyaniline and its derivatives enhanced the [Ru(bpy)₂(picCOOH)]²⁺.(ClO₄⁻)2 absorption band, photoluminescence and fluorescence lifetime. The enhancement observed from interaction of [Ru(bpy)₂(picCOOH)]²⁺.(ClO₄⁻)₂ with polyaniline and its derivatives might be due to the excited state electron transfer from the PANI and PANSA excited state to the [Ru(bpy)₂(picCOOH)]²⁺.(ClO₄⁻)₂. It was further demonstrated in this work that it is possible to form polyaniline and PANSA doped with [Ru(bpy)₂(picCOOH)]²⁺.(ClO₄⁻)₂ films on ITO electrode using potentiostatic growth method to favour ECL production. The results showed that all films generated ECL in the presence of Tripropylamine (TPA) as a co-reactant and their emission properties depend on time used to prepare the film. The enhancement of ECL signal was due to a positive electron transfer from the conducting polymer (PANI and PANSA) to [Ru(bpy)₂(picCOOH)]²⁺.(ClO₄⁻)₂ complex. The results highlighted the potential of these polymeric luminophores usage in the manufacturing of the ECL devices.

Thienoacenes represent an intriguing class of organic semiconducting molecules with potential applications in organic electronics. Some of thienoacenes have been reported with high charge carrier mobility in organic field-effect transistors (OFET). OFETs based on naphtho[2,1-b:3,4-b’]dithiophene (NDT) exhibited moderate device performance and low-band gap donor-acceptor copolymers based on NDT showed a promising solar power conversion efficiency. In this thesis, four novel series of thienoacenes based on naphtho[2,1-b:3,4-b’]dithiophene backbone were designed and synthesized for OFET applications. Firstly, a novel series of p-type semiconducting naphthodithieno[3,2-b]thiophene derivatives (NDTT-n) composed of six-fused aromatic rings were designed and synthesized (Figure 1). The OFETs based on NDTT-10, and NDTT-12 fabricated by vacuum deposition showed a hole mobility of 0.22 and 0.13 cm2/(Vs), respectively with Ion/Ioff above 107 after annealing at 80 oC. Secondly, the derivatives of NDT fused with benzene rings at the flanks of thiophene, namely NBBT-n (Figure 2) were also designed and synthesized. OFETs based on NBBTF-10 fabricated by vacuum deposition exhibited a hole mobility of 0.35 cm2/(Vs) with a current on/off ratio of 106 107 after annealing at 160 oC. Further extension of π-conjugation of NDTT by incorporating with fused thiophenes leading to a new NBTBT-n series was also developed (Figure 3). The OFETs fabricated by NBTBT-10 showed the hole mobility up to 0.25 cm2/(Vs) with a current on/off ratio of 105 106 after annealing at 220 oC. Lastly, two dimensionally π-extended, butterfly-shaped thienoacenes (Figure 4) were also synthesized. The OFETs based on SMB-10 fabricated by spin-coating showed the best performance in this series with an average mobility of 0.027 cm2/(Vs) for five devices and the highest mobility of 0.038 cm2/(Vs) with a current on/off ratio of 106 107 by from chloroform. Key words: organic semiconducting molecules, organic field-effect transistor, thienoacene, charge carrier mobility.

No description available.

The study of the new materials potentially usable for organic photovoltaic and electronics are getting very important from the point of ecological and financial view. Organic electronic devices are getting more and more popular and it is only up to us to search for the new ones that are able to improve their physical properties. The aim of this thesis is to search for materials like have been mentioned above which have very good semiconducting properties. Solutions of pure materials and its mixtures with different concentrations of fullerene have been investigated by ultra-violet spectroscopy, classical fluorescence and time resolved spectrometry. Mainly, were studied the influence of the central atom and side substituents for the optical and electronical properties of our materials of interest. With adding fullerene was observed quenching phenomena of the fluorescence, because all these new materials show usually high photoluminescence. Based on the given results, the most suitable materials had been chosen to provide trial of making organic solar cell, and therefore investigated by the mean of electric measurements (direct current).