Birefringence induced by the orientation of polymer main chains during an injectionmolding or extrusion processing restricts the application of optical polymers to optical devices that require maintaining the polarization state of incident light. We propose the “birefringent crystal dopant method” to compensate the birefringence of polymers by homogeneous doping with an opposite birefringent needle-like crystal. Strontium carbonate (SrCO3) was selected for this method and synthesized, with particle lengths of 50-200nm and aspect ratios of 2-5. SrCO3 was doped into poly(MMA/BzMA= 78/22(wt./wt.)) film. The film was uniaxially drawn at 130°C and 4mm/min. For the first time, the positive birefringence of the drawn copolymer film at a wavelength of 633nm was compensated by doping with 0.3wt.% of SrCO3 without losing transparency and thermostability.

In an operating LED, electrons are injected into the polymer's LUMO level from the cathode and holes from the anode into the polymer's HOMO level. The value of the electron affinity (EA) is usually inferred (often incorrectly) from the experimental HOMO level energy and the value of the optical band gap. Using carefully controlled experimental conditions we can now directly access the EA position. Reduction events have been observed on poly(9,9-dioctylfluorene) (F8) and blue emitting polymers based on 9,9-dioctylfluorene. This event is consistent and reversible. As predicted by theory, the LUMO level is entirely delocalised over F8 blocks. An EA of approx. –2.3eV, equal to that of F8, is therefore a common feature of blue polymers containing sequences of 9,9-dioctylfluorene. Blue emitting 9,9-dioctylfluorene -triarylamine AB copolymers containing either 4-sec-butylphenyl diphenyl amine (TFB) or N,N'-bis(4-butylphenyl)-N,N'-diphenyl phenylenediamine (PFB) are characterized by an electron affinity of –2.1eV. This result shows that the LUMO wave function in these systems is localized on the Ph-F8-Ph units. In the case of PFB homopolymer the LUMO level is again localized, this time on the biphenyl unit at the junction of each 2 repeating units. The EA for this material is therefore lower than in the previous cases: -1.84eV, as a result of the increased localization of the LUMO wave function Electrochemical characterisation provides a direct probe for the dynamic of the charge injection in a polymer system, as the HOMO and LUMO are the states into which the holes and electrons are injected. Electrochemical measurement together with theoretical modelling gives a more complete understanding of molecular properties and behaviour. However, electrochemical measurements are not necessarily relevant to the optical energy gap, as the optical excitation does not necessarily involve molecular orbitals probed by electrochemical methods.

In order to tailor the synthesis of new robust organic materials for electronic applications and to guarantee the required life time for the emerging commercial plastic electronic applications it is of key importance to understand the underlying degradation mechanisms. Since plastic electronics is a rather young technology introducing new material systems, its reliability is characterized by new failure and degradation mechanisms, a relatively high amount of early failures and multi-modal failure distributions. To understand the mechanism responsible for a given failure or degradation mode, it is essential to study it separately, through appropriate test structures and test techniques. Powerful techniques for this purpose are a.o. analytical techniques (SEM, TEM, SPM,..), in-situ electrical measurement techniques and spectroscopical techniques (in-situ FTIR, in-situ UV-Vis, PDS). The benefits of these in-situ techniques in the reliability study of organic based electronics will be illustrated in this contribution.

Nanocrystalline semiconductor particles exhibit a size dependent bandgap emission, due to size quantisation effects. These particles are derived from solution chemistry and can be made monodisperse under the right synthesis conditions. Compared to organic materials, the inorganic nanoparticles show much higher stability against oxidation and degradation, which makes them an interesting candidate for LEDs and displays. So far, LEDs based on semiconductor nanoparticles typically included low stability organic materials to provide charge injection. The talk will present a new class of nanoparticle LEDs, made without sensitive organic materials. These LEDs show high efficiencies, well defined color throughout the red to green part of the visible spectrum and improved stability under ambient conditions without excessive encapsulation. Using high quality monodisperse suspensions, high color purity is achieved for the emission which paves the road to cheap, high quality displays based on inorganic semiconductor nanoparticles.

We describe and demonstrate a micromachined shadowmask that allows the realization of intra-grain and oligo-grain top-contact organic thin film transistors (OTFTs). First experimental results of OTFT's show that for small channel lengths, grain boundary barriers indeed appear to dominate the output characteristics of OTFTs.

The emission wavelength in conjugated copolymers is determined by the various monomers used, their sequence in the polymer backbone, the effective conjugation length of the material, and intra- and intermolecular interactions of the different units. This paper will discuss the influence of conjugation length as well as the influence of intramolecular charge-transfer on the absorption and emission properties. Fluorene, benzothiadiazole and a third comonomer (fluorene, xylene or triphenylamine) were used as building blocks. The influence of monomer sequence is probed as well by comparing sequentially random copolymers to their sequentially defined ones with identical monomer ratios. Model oligomers were also made for comparison.

We demonstrate here balancing between hole and electron injection in bilayer organic tris(8-hydroxyquinoline)aluminum (Alq3) based electroluminescent (EL) devices by measuring current-voltage (I-V) characteristics of single-carrier devices with different thickness and by comparing the device performance with various chemically modified ITO. We measure I-V characteristics due to holes in hole-only bilayer devices with various modified ITO anodes and those due to electrons in electron-only single-layer devices with C6H5COOLi(2 nm)/Al cathode. Here, hole-only devices are those, in which only holes are carriers and the current due to electrons is negligible. We found that the I-V characteristics observed for the hole-only bilayer devices with UV-ozone and ClC6H4COCl treated ITO were comparable to the I-V characteristics for the electron-only single-layer device of ITO(as-cleaned)/Alq3(150 nm)/C6H5COOLi(2 nm)/Al. In other words, hole and electron injections are well balanced when we use UV-ozone and ClC6H4COCl treated ITO anodes. EL characteristics have shown that luminance decreased clearly for bilayer organic EL devices with an Al cathode where electron injection was not enhanced significantly. The decrease in EL efficiency can be attributed to unbalanced hole and electron injection. The unbalanced injection results in excess of one carrier type that does not contribute to light emission, and results in deactivation of 1Alq3 at high currents due to quenching 1Alq3 by large excess of Alq3+. in the emission zone.

Au/fullerene(C60)/SiO2/Si field effect transistor (FET) has been investigated to examine the behavior of carrier injection by using displacement current measurement (DCM) and infrared absorption spectroscopy in the multiple internal reflection (MIR-IRAS). At the first scan of DCM, an increasing displacement current due to electron injection was clearly observed above a threshold voltage in forward scan, while no flow-back of the injected electrons was observed, indicating that almost all electrons injected in the scan were trapped. The capacitance obtained from the increasing current suggests that the electrons injected from a Au electrode spread laterally along C60/SiO2 to some extent. At the further scans of DCM, the threshold voltage was shifted to higher voltage, and the lateral spread of the electron was quite suppressed due to the space charge of the filled traps. These results clearly demonstrate that DCM is a useful method to examine the behavior of carriers in field effect transistor (FET) devices. The spectral change in MIR-IRAS observed under bias voltage for electron injection is also reported.

We have studied photovoltage spectra of PPV thin films using both conventional single layer LED structure (ITO/PPV/Al), and capacitive structure consisting of ITO/Mica/PPV/ITO films. The photovoltage spectra for both types of devices have sharp features and are identical indicating that the features observed are primarily due to PPV material itself. We observed two sharp peaks in the energy range of 2.5 -2.7 eV (i.e. above HOMO-LUMO gap) in photovoltage spectrum. The lineshape of the peaks strongly suggests that the peaks are most probably associated with photoionization of excitons. Temperature dependence of spectral lineshape of photocurrent peaks has been studied in the range of 80K-300K. The magnitudes of photocurrent peaks are weakly dependent on temperature, while other spectral features such as peak position and peak width are nearly independent of temperature. On the basis of absorbance, photovoltage and PL spectra, we conclude that both polarons and photoionization of excitons contribute to steady state photovoltage spectra.

A set of six new two-photon engineered diethylamino-substituted styryl pyrazine (DEASP) dyes have been developed as chemically responsive chromophores. This work employs UV/Vis spectroscopy to draw structure-optical property relationships and to quantify the solvatochromic effect observed for these dyes. Absorbance profiles for each of these dyes have been measured in 22 solvents ranging from very nonpolar (TMS) to very polar (water). Absorbance maxima of the longest wavelength π→π transitions have been correlated to nine empirical scales of solvent polarity, and a comparative analysis is presented. Dimroth & Reichardt's and Kamlet & Taft's single parameter scales have been recalculated with spectral data obtained for the six DEASP dyes. The correlation of these established and recalculated scales are shown and discussed. DEASP chromophores are found to exhibit high sensitivity to their chemical environment and exceptional range as solvatochromic probes. Current models of solvatochromism, based on dipolar probes, cannot account for the solvatochromism observed in our quadrupolar dyes, and fail to describe the effect of the chemical environment on this family of twophoton dyes. The need to develop a more universal model of solvation incorporating higher order moment contributions is apparent.

Electronic structure calculations for the mer and fac-isomers of aluminum tris (8-hydroxyquinoline) (Alq3) and the methyl-substituted series, nMeq3Al (n = 3 - 7) are presented. From these data, we estimate their relative abundances in Alq3 thin films and the resultant trap state energies. Ab initio computations performed at the SCF level suggest a significantly higher stability (6 - 7.5 kcal/mol) of the mer-isomer over the facial form, whereas MP2 treatment of electron correlation effects lowers the difference to (4 - 4.5 kcal/mol). Substitution of the Al+3 metal ion with the larger ions Ga+3 and In+3 increases the energetic preference of the meridianal form by 2.7 kcal/mol and decreases it by 0.8 kcal/mol, respectively. Trap state energies calculated by previously proposed methodologies show little difference between mer and fac trap states. These results suggest that the existence of the facial isomer in thin films of metal trisquinolates is unlikely to significantly affect charge conduction.

The performance of the semiconducting component in organic field effect transistors (OFET's), is a key parameter in the advancement of organic electronic devices. This work describes the development of solution processible liquid crystalline semiconductors, both main chain rigid rod polymers and small molecule polymerisable liquid crystals, referred to as reactive mesogens. New conjugated main chain polymeric semiconductors have been designed, synthesised, and their performance in transistor devices is reported. Small molecule liquid crystalline semiconductors, which contain reactive end groups, were also prepared, and their design, characterisation, and performance in transistor devices is discussed.

Luminescence quenching experiments on oriented and drop-cast poly(phenylene vinylene), (PPV), films identify the excitons in these polymer films as Wannier-Mott excitons. The data are interpreted in terms of a distribution of exciton binding energies (Eb). We find that the width of this distribution is well correlated with the degree of structural disorder. The relatively small mean EbEb, approximately 60 meV, results in field-induced exciton disociation that limits the quantum efficiency obtained from polymer-based light emitting diodes (PLEDs) which typically are operated at applied fields of 106 V/cm or greater where the field-induced exciton disociation is significant. We present data and analysis that support these conclusions, as well as a discussion on the implications of our findings on polymer-based display technology.

Structures based on combination of electrically conductive polymers with inorganic semiconductors are currently intensively investigated with the aim to prepare low-cost, largearea and flexible photovoltaic devices. In this study, multilayer structures consisting of CuInS2 (CIS) and poly(3,4-ethylenedioxythiophene) (PEDOT) doped with polystyrenesulfonate (PSS) thin films were prepared and investigated for photovoltaic applications. Polycrystalline CIS absorber layers were synthesized on top of a layered structure on Cu tape substrate using socalled non-vacuum CISCuT technique. Thin PEDOT buffer layers doped with PSS were deposited onto KCN etched and vacuum annealed CIS films. The deposition was performed using the spin-casting technique from an aqueous dispersion of PEDOT/PSS mixed with Nmethylpyrrolidone, isopropanol, glycerin and epoxysilane additives. Optimal deposition parameters for stable PEDOT films with a good adherence to the surface of CIS were selected experimentally. The morphology and thickness of prepared films and structures was determined using SEM technique. Average film thickness was about of 1.5 μm for CIS and 50 nm for PEDOT films. Current-voltage and impedance characteristics were measured. Significant photovoltage and photocurrent of the photovoltaic structures were observed under standard illumination intensity. The best structure showed an open-circuit voltage of 510 mV and a shortcircuit current density of 20.2 mA/cm2.

The patterning of conjugated polymers for multicolored electroluminescence applications is a current topic of research in polymer device technology. Several techniques including direct writing approaches such as ink-jet printing have been proposed to solve this challenge. We present an approach to tuning the (electro)luminescence color of a film consisting of a blend of conjugated polymers after its deposition by means of UV-irradiation in the presence of an active agent. This promises to be an alternative, highly parallel approach towards multicolored electroluminescence.

A diversified family of 2,5-dihydrofuran derivatives has been synthesized as a new class of highly efficient and tunable electron acceptors using the single-mode focused microwave irradiation. High poling efficiency and very large electro-optic coefficients (r33 values of 128 and 116 pm/V at 1.3 μm) have been demonstrated using 2-dicyanomethylen-3-cyano-4,5,-dimethyl-5-trifluoromethyl-2,5-dihydrofuran (CF3-TCF)-based chromophores as dopant in poly(methyl methacrylate) (PMMA) and a high glass-transition temperature polyquinoline (PQ-100) respectively. Excellent dipole alignment stability has also been demonstrated in the guest/host composite at 85°C. Multi-functionalized NLO chromophores based on hydroxy containing 2,5-dihydrofuran acceptors were also synthesized through microwave methodology for further characterizations.

The electrosynthesis of poly (3, 4-ethylenedioxythiophene) from its monomer 3, 4-ethylenedioxythiophene with doping by a mixture of lithium tosylate and co-surfactants sodium dodecylsulfate and sodium poly (4-styrenesulfonate) was performed. An anionic surfactant in aqueous solution was used to increase monomer solubility in water and reduce the potential oxidation relative to acetonitrile medium. Polymer films were synthesized by cyclic voltammetry and galvanostatic methods and characterized by IR, AFM and SEM spectroscopy.

Charge transport in poly(3-hexylthiophene) field effect transistors has been studied in a series of devices with channel lengths ranging from 3 μm down to 200 nm over a broad range of temperatures and gate voltages. We report gate-modulated highly nonlinear transport at temperatures below ∼200 K that is consistent in form with a Poole-Frenkel-like hopping mechanism in the space charge limited current regime. There is also consistency between this behavior and the hypothesis that density of localized states is strongly energy dependent. We also observe what appears to be a crossover from thermally activated to nonthermal hopping below 30 K.

Thin films of low molecular weight electroluminescence (EL) materials, Alq3 (aluminum tirs-8-hydoroxyquinline), TPD (N,N'-diphenyl-N,N'-bis (3methylphenyl)-(1,1'-biphenyle)-4, 4'-diamine) were deposited by pulsed laser ablation (PLA) method using KrF excimer laser and Nd:YAG laser. Optical absorption property, surface morphology and photoluminescence of the films were investigated. Alq3 films by Nd:YAG laser show slight absorption at around 400 nm, and TPD films by either KrF laser or Nd:YAG laser showed absorption at 320 nm and 360 nm. It was found that TPD thin films for EL devices can be deposited by PLAmethod usig Nd:YAG laser.

We have investigated the effects of white-light illumination on the electrical performance of organic polymer thin-film transistors (OP-TFTs). The OFF-state drain current is significantly increased, while the drain current in the strong accumulation regime is relatively unaffected. At the same time, the threshold voltage is decreased and the subthreshold slope is increased, while the field-effect mobility of the charge carriers is not affected. The observed effects are explained in terms of the photogeneration of free charge carriers in the channel region due to the absorbed photons.