ABSTRACT Light emitting diodes of non-fully conjugated coil-like homopolymers and fully conjugated rigid-rod homopolymers with electron withdrawing or donating group were studied. A series of Poly[2,2-(m-2-X-phenylene)-4-4¡A-hexafluoroisopropane- bibenzoxazoles] (6F-PBO-X, with X = amine, hydrogen and nitro) and poly-p-(2-X- phenylene)-benzobisoxazole (PBO-X, with X = amine, hydrogen and nitro) were synthesized for light emitting diode applications to observe electroluminescence emission affected by electron withdrawing or donating group. All polymers were fabricated identically to form bi-layer light emitting diodes. In the devices, poly(3,4-ethylenedioxythiophene):poly(styrenesulfonite)(PEDOT:PSS) was applied to be a hole transport layer; indium tin oxide (ITO) was the anode; and aluminum was the cathode. Devices of the non-fully conjugated coli-like polymers (6F-PBO-X) and the fully conjugated rigid-rod polymers (PBO-X) all showed threshold voltage about 4 V. In the electroluminescence (EL) spectrum, the maximum intensity of non-fully conjugated polymer (6F-PBO-X) with amine (-NH2), hydrogen (-H) or nitro (-NO2) functional group was at 499 nm, 505 nm and 515 nm, respectively, showing a 20 nm wavelength shift. From ¡VNH2, -H and ¡VNO2 groups, their Commission International de l`Eclairage (C. I. E.) coordinates were (0.30, 0.46), (0.34, 0.45) and (0.40, 0.46), respectively. The EL maximum intensity for fully conjugated rigid-rod polymer PBO-X was at 521 nm (-NH2) and 474 nm (-NO2) showing a 50 nm wavelength shift. Their C. I. E. coordinates were (0.42, 0.45) and (0.25, 0.38), respectively. This is attributed to the fully conjugated, collinear, coplanar, rigid-rod polymers (PBO-X) backbone readily affected by the push-pull functional groups showing a large red shift.

Conjugated polymers and oligomers are great materials for use in the next generation devices namely organic field effect transistors, light emitting diodes and polymeric solar cells. Apart from having the potential for developing power-efficient, flexible, robust and inexpensive devices, conjugated polymers can also be tuned by molecular design to optimize device characteristics. One key problem for the full commercial exploitation of conjugated polymers is that the charge carrier mobility of the state-of-the-art polymer semiconductors is much lower than required for many applications. The performance of the devices is strongly dependent on the molecular structure and supermolecular assembly of the conjugated polymer chains. This thesis covers our attempts to design molecular structure to control and improve the solid state properties of conjugated polymers. The relative placement of side chains along the backbone has a great influence on the solid state ordering of conjugated polymers. Poly(2,5-disubstituted-1,4-phenylene ethynylene)s (PPE)s, an important class of conjugated polymers, are generally synthesized by Pd-catalyzed coupling polymerizations of appropriately substituted diiodo and diethynyl benzenes (i.e., A-A and B-B type monomers). In asymmetrically substituted PPEs, this results in an irregular substitution pattern of the side chains along the polymer backbone. We report a new synthetic approach to prepare regioregular unsymmetrically substituted PPEs by polymerization of 4-iodophenylacetylenes (i.e., A-B type monomer). We provide a detailed discussion of various approaches to the synthesis of PPEs with different regioregularities and provide a description of the differences between regioregular and regiorandom analogs. The effect of regioregularity becomes even more important when the two side chains are very dissimilar or amphiphilic. We explore the effect of relative placement hydrophobic (dodecyloxy) / hydrophilic (tri(ethylene glycol) and hydrophobic (dodecyloxy)/fluorophilic (fluoroalkyl) side chains along the poly(1,4-phenylene ethynylene) backbone. We found that the regioregular substitution of the polymer backbone provides a structure in which the side chains segregate to afford a Janus-type structure. The regioregular polymer chains pack more densely in a monolayer at the air-water interface, and pack into a bilayer in the solid state to form a highly crystalline material. Pentacenes are very important organic molecules for use as semiconductor in oFETs due to their low band gap and high field effect mobility. One approach to reduce the bandgap of a polymeric system and improve performance is to include low bandgap small molecules into the conjugated backbone. A new copolymer system consisting of pentacene and terthiophene was developed and its optical and electronic properties along with its stability were evaluated. We report the use of ultrasonication of P3HT as a novel operationally-simple process to significantly improve the field effect mobility of P3HT-based FETs, thereby potentially eliminating the need for dielectric surface modifications or further processing of the device. Investigation of the sonicated polymer samples by number of characterization techniques indicates that ultrasonication leads to aggregation and ordering of the P3HT chains resulting in increase in the mobility.

GaN-based light emitting diodes (LEDs) face several challenges if the technology is to make a significant impact on the solid state lighting market. The two most pressing of these challenges are cost and efficiency. The development of alternative substrate technologies shows promise toward addressing both of these challenges, as both GaN-based device technology and the associated metalorganic chemical vapor deposition (MOCVD) technology are already relatively mature. Zinc oxide (ZnO) and silicon (Si) are among the most promising alternative substrates for GaN epitaxy. This work focuses on the development of MOCVD growth processes to yield high quality GaN-based materials and devices on ZnO and Si. ZnO, because of its similar lattice constant and thermal expansion coefficient, is a promising substrate for growth of low defect-density GaN. The major hurdles for GaN growth on ZnO are the instability of ZnO in a hydrogen atmosphere and out-diffusion of zinc and oxygen from the substrate. A process was developed for the MOCVD growth of wurtzite GaN and InxGa1-xN on ZnO, and the structural and optical properties of these films were studied. High zinc and oxygen concentrations remained an issue, however, and the diffusion of zinc and oxygen into the subsequent GaN layer was studied more closely. Silicon is the most promising material for the development of an inexpensive, large-area substrate technology. The challenge in GaN growth on Si is the tensile strain induced by the lattice and thermal mismatch between GaN and Si. A thin atomic layer deposition (ALD)-grown Al2O3 interlayer was employed to relieve strain while also simplifying the growth process. While some strain was still observed, the oxide interlayer leads to an improvement in thin film quality and a reduction in both crack density and screw dislocation density in the GaN films. A comparison of GaN-based LEDs grown on sapphire and Al2O3/Si shows similar performance characteristics for both devices. IQE of the devices on silicon is ~32%, compared to ~37% on sapphire. These results show great promise toward an inexpensive, large-area, silicon-based substrate technology for MOCVD growth of GaN-based optoelectronic devices.

For organic electronic device applications materials are needed which display good charge carrier mobility, good processability, and stability towards oxygen and moisture. Alkynylated N-Heteroacenes fulfill many of these requirements. Substitution with alkyne groups as well as the introduction of the pyrazine subunit both inhibits oxidative degradation at sensitive position in the molecules. Additionally the trialkylsilylethynyl group aides in directing the packing motif as well as vastly increases the solubility over unsubstituted analogues. A requisite precursor in the synthesis of alkynylated N-heteroacenes is alkynylated acenothiadiazoles. These thiadiazoles display interesting photophysical properties and can be functionalized to produce a wide range of properties in closely related materials. The acenothiadiazoles themselves have potential applications as an N-type semiconductor. Optical gaps and calculated HOMO-LUMO gaps show that these molecules, when compared to known N-type materials, should be easily injected with electrons. Additionally the crystal packing of these compounds shows favorable π-orbital overlap which should provide excellent charge carrier mobilities.

Core-shell nanowire LEDs are light emitting devices which, due to a high aspect ratio, have low substrate sensitivity, allowing the possibility of low defect density GaN light emitting diodes. Current growth techniques and physical non-idealities make the production of high conductivity p-type GaN for the shell region of these devices difficult. Due to the structure of core-shell nanowires and the difference in conductivity between ntype and p-type GaN, the full junction area of a core-shell nanowire is not used efficiently. To address this problem, a series of possible doping profiles are applied to the core of a simulated device to determine effects on current crowding and overall device efficiency. With a simplified model it is shown that current crowding has a possible dependence on the doping in the core in regions other than those directly in contact with the shell. The device efficiency is found to be improved through the use of non-constant doping profiles in the core region with particularly large efficiency increases related to profiles which modify portions of the core not in contact with the shell

This thesis focuses mainly on the techniques to achieve high-performance top-emitting OLEDs, regarding device efficiency and lifetime for both non-inverted and inverted structures. It is thus organized as follows: In Chapter 2, the basic physics of organic semiconductor materials are reviewed, including the electronic properties of organic semiconductor materials, molecular excitations and their electronic transitions etc., which are believed to be critical for understanding of the work. Then, the general device physics of OLEDs are reviewed in detail, which includes almost every important electrical and optical process involved in the device. Finally, techniques and methods used to improve the device performance are summarized, which includes electrical doping of charge carrier transport layers. In Chapter 3, all organic materials, experimental techniques, and characterization methods used in this study are briefly described. In the following Chapter 4, techniques that are used for device optimization of non-inverted top-emitting OLEDs are discussed. Also, the mechanism of light outcoupling enhancement by a capping layer is discussed there. In the last part of Chapter 4, the influence of the optical device structure on the intrinsic quantum yield of the emitters is studied. Chapter 5 is focused on inverted top-emitting OLEDs, which are believed to be better applicable with current mainstream n-type amorphous silicon thin film transistor (TFT) technology. In this Chapter, the organic/metal and metal/organic interfaces are investigated in detail and their influence on device performance is discussed. In Chapter 6, the degradation of top-emitting OLEDs is studied, with a focus on the influence of electrode material and electrode thickness on the lifetime of top-emitting devices.

The electronics industry today is one that stands as a multi-billion dollar industry that is increasingly incorporating more and more products that have ever escalating applications in our everyday life. One of the main sectors of this industry, and one that is likely to continue expanding for a considerable number of years are flat-panel displays. Traditionally, the displays market has been dominated by cathode ray tube (CRT) and liquid crystal displays (LCDs) display types. The drawback of such display displays is that they can be bulky, heavy and/or expensive and so there is considerable room for an alternative and superior technology. One possibility is organic semiconductor displays where light-emitting molecules can be dissolved in common solvents before being inkjet printed, spin-coated or even painted onto any surface giving the benefits of simple and cost effective processing. Organic light-emitting diodes (OLEDs) have recently become ever more evident as a major display type. This thesis focuses on the advancement of light-emitting dendrimers towards flat-panel display applications. The particular interest in dendrimers arises because it has been found they are capable of giving solution-processed phosphorescent devices with high efficiency. Throughout the thesis the benefits of the dendrimer concept are repeatedly shown revealing why this could become the ideal organic material for display applications. The thesis introduces various techniques of electroluminescence and photoluminescence measurements before applying such methods to study a large number of light-emitting dendrimers in order to explore the role of intermolecular interactions, how they are related to molecular structure, and how this determines photophysical and charge transporting properties of the dendrimers. By such studies a number of highly efficient solution-processed phosphorescent light-emitting dendrimers have been identified while the efficiency of devices made from these dendrimers has been improved. This has been demonstrated in each of the three primary display colours of red, green and blue. The work detailed thus brings closer the prospect of dendrimer light-emitting diodes being the future flat-panel display type of choice.

Spontaneous parametric down conversion (SPDC) – incoherent light scattering – is one of the main entangled photons source applied in quantum optics experiments. The tradition to pump SPDC by laser radiation was established from the very first SPDC experiments in 1968. The aim of this thesis was experimentally to investigate the ability to generate an SPDC pumping by both temporal and spatially incoherent radiation - a high-power blue LED. Weak SPDC signals were registered with high sensitivity CCD cameras, photons coincidences were detected with photon counters. The theoretical simulations were performed in parallel with experiments. Therefore, mathematical simulation code was written in order to estimate the SPDC power distribution and simulate photon coincidence experiment changing the properties of pump beam and detection system. Experimental results reveal that incoherent light sources can be good alternative for the laser systems in order to generate average quality biphoton fields especially in those experiments in which low biphoton field coherency would be advantage. The main advantages of the incoherent sources over laser systems are low cost, simple production technology and the huge commercial variety of different wavelength sources. / Parametrinė fluorescencija (PF) – nekoherentinė šviesos sklaida – yra vienas pagrindinių susietųjų fotonų šaltinių taikomų kvantinės optikos eksperimentuose. Nuo pat pirmųjų PF eksperimentinių tyrimų 1968 metais įsigalėjo tradicija šį reiškinį žadinti išimtinai lazerine spinduliuote. Šios disertacijos tikslas – eksperimentiškai ištirti galimybę generuoti PF tiek laikiškai, tiek ir erdviškai nekoherentine spinduliuote – didelės galios šviesos diodu. Atliekant tyrimus didelio jautrio CCD kamera buvo registruojami silpni PF signalai, pavienių fotonų skaitliukais buvo registruojami fotonų sutapimai,. Lygiagrečiai eksperimentiniams tyrimams buvo atliekami teoriniai skaičiavimai. Šiuo tikslu buvo parašytas matematinio modeliavimo programinis kodas, skirtas įvertinti PF erdvinį galios pasiskirstymą bei modeliuoti fotonų sutapimų eksperimentą, keičiant kaupinimo pluošto ir detekcijos sistemos savybes. Šio darbo rezultatai atskleidžia, kad nekoherentiniai šaltiniai gali būti puiki alternatyva lazerinėms sistemoms siekiant žadinti vidutinės kokybės dvyninius laukus, ypatingai tokiose tyrimų srityse, kuriose mažas dvyninio lauko koherentiškumas būtų didžiulis privalumas. Pagrindiniai nekoherentinių šaltinių pranašumai prieš lazerines sistemas: maža kaina, paprasta gamybos technologija ir didžiulė komercinė skirtingo bangos ilgio šaltinių įvairovė.

Parametrinė fluorescencija (PF) – nekoherentinė šviesos sklaida – yra vienas pagrindinių susietųjų fotonų šaltinių taikomų kvantinės optikos eksperimentuose. Nuo pat pirmųjų PF eksperimentinių tyrimų 1968 metais įsigalėjo tradicija šį reiškinį žadinti išimtinai lazerine spinduliuote. Šios disertacijos tikslas – eksperimentiškai ištirti galimybę generuoti PF tiek laikiškai, tiek ir erdviškai nekoherentine spinduliuote – didelės galios šviesos diodu. Atliekant tyrimus didelio jautrio CCD kamera buvo registruojami silpni PF signalai, pavienių fotonų skaitliukais buvo registruojami fotonų sutapimai,. Lygiagrečiai eksperimentiniams tyrimams buvo atliekami teoriniai skaičiavimai. Šiuo tikslu buvo parašytas matematinio modeliavimo programinis kodas, skirtas įvertinti PF erdvinį galios pasiskirstymą bei modeliuoti fotonų sutapimų eksperimentą, keičiant kaupinimo pluošto ir detekcijos sistemos savybes. Šio darbo rezultatai atskleidžia, kad nekoherentiniai šaltiniai gali būti puiki alternatyva lazerinėms sistemoms siekiant žadinti vidutinės kokybės dvyninius laukus, ypatingai tokiose tyrimų srityse, kuriose mažas dvyninio lauko koherentiškumas būtų didžiulis privalumas. Pagrindiniai nekoherentinių šaltinių pranašumai prieš lazerines sistemas: maža kaina, paprasta gamybos technologija ir didžiulė komercinė skirtingo bangos ilgio šaltinių įvairovė. / Spontaneous parametric down conversion (SPDC) – incoherent light scattering – is one of the main entangled photons source applied in quantum optics experiments. The tradition to pump SPDC by laser radiation was established from the very first SPDC experiments in 1968. The aim of this thesis was experimentally to investigate the ability to generate an SPDC pumping by both temporal and spatially incoherent radiation - a high-power blue LED. Weak SPDC signals were registered with high sensitivity CCD cameras, photons coincidences were detected with photon counters. The theoretical simulations were performed in parallel with experiments. Therefore, mathematical simulation code was written in order to estimate the SPDC power distribution and simulate photon coincidence experiment changing the properties of pump beam and detection system. Experimental results reveal that incoherent light sources can be good alternative for the laser systems in order to generate average quality biphoton fields especially in those experiments in which low biphoton field coherency would be advantage. The main advantages of the incoherent sources over laser systems are low cost, simple production technology and the huge commercial variety of different wavelength sources.

Organic electronic devices are receiving growing interest because of their potential to employ lightweight, low-cost materials in a flexible architecture. Typically, indium tin oxide (ITO) is utilized as the transparent positive electrode in these devices due to its combination of high transmission in the visible spectrum and high electrical conductivity. However, ITO may ultimately hinder the full market integration of organic electronics due to its increasing cost, the limited availability of indium, lack of mechanical flexibility, and sustainability with regards to the environment and material utilization. Therefore, alternatives for ITO in organic electronics are currently being pursued. Transparent electrodes comprised of single wall carbon nanotubes (SWNTs) are an appealing choice as a surrogate because of the extraordinary electrical and mechanical properties these 1-D structures posses. As such, the research presented in this dissertation has been conducted to advance the goal of manufacturing SWNT networks with transparent electrode properties that meet or exceed those of ITO. To this end, SWNT films were characterized with regard to the collective and individual optoelectronic properties of the SWNTs that comprise the network. Specifically, corroborative theoretical and experimental observations were employed to expand the understanding of how the optoelectronic properties of polydisperse and monodisperse SWNT networks are enhanced and sustained through chemical treatment and subsequent processing. In addition, the impact of interfacial electrical contact resistance between SWNT electrodes and metallic fingers often used in photovoltaic system applications was elucidated. In summary, the research presented in this dissertation can be leveraged with present state of the art in SWNT films to facilitate future SWNT electrode development.