ABSTRACT Optoelectronics of polymer light emitting diode (LED) depends significantly on polymer molecular structure and charge conjugation. This study focused on the optoelectronics of freestanding films and LEDs of a colinear, fully conjugated heterocyclic aromatic rigid-rod polymer (PBT) and its mixtures with a partially conjugated coil-like polymer (Pbi). A deuterated PBTd4 was also mixed with a fully conjugated coil-like polymer (ABPBI) for UV-Vis absorption spectrum, photoluminescence (PL), diodic current-voltage response, and electroluminescence (EL). Rigid-rod PBT was only soluble in strong protic acid. PBT films were processed using methanesulfonic acid. PBT free-standing films showed maximum absorptions at 468 nm and 640 nm; PBTd4 having all hydrogen atoms on the phenylene moiety substituted by deuterium retaining same electron orbitals thus showed same absorption and PL spectra. It was likewise for the PBTd4 and ABPBI mixtures at ABPBI concentrations of 1 % and 10 %. For mixtures of PBT and Pbi, the absorption spectra indicated super- position of individual optical absorption response and no energy transfer. However, PL spectra showed a blue shift with increasing Pbi content. This was attribed for PBT rod-like configuration, or PBT aggregation perturbed by mixing with Pbi. Monolayer LED of Al/PBT/ITO and Al/Pbi/ITO yielded a threshold voltage of 4 V. When PBT/Pbi mixtures of 75/25, 50/50, 25/75, were used as the light emitting layer, the threshold voltage altered to 10 V, 7 V and 17 V, respectively. This threshold voltage deviation from 4 V is due mainly to difference in layer thickness, or phase separation affecting the tunneling effect. To enhance LED stability, an Ag layer was evaporated onto the Al electron injection electrode. For Ag/Al/PBT/ITO devices and mixed PBT/Pbi (75/25,50/50,25/75) devices, the maximum EL wavelength exhibited no systematic change at 753 nm, 714 nm, 727 nm, and 697 nm, respectively, due to using different bias voltage.

Polymer light emitting diodes (PLED) were using a heterocyclic aromatic rigid-rod polymer poly-p-phenylene-benzobisoxazole (PBO) as an opto-electronically active layer; and poly(3,4-ethylenedioxythiophene):poly(4-styrenesulfonic acid) (PEDOT:PSS) as a hole transporting layer. Aluminum (Al) and indium tin oxide (ITO) were served as device cathode and anode, respectively. [6,6]-phenyl C61-butyric acid methyl ester (PC61BM) or derivatized multi-wall carbon nano-tube (MWCNT-C18), with great electron transporting ability, was doped into PBO to enhance the performance of PLED devices as well as the thin-film electrical conductivity. The optical length was changed by using different spin coating speeds and durations. From the research, the £fmax of electroluminescence (EL) was blue-shifted as PEDOT:PSS spin coating speed increased for a thinner layer. Once using a higher spin coating speed repeatedly to coat PEDOT:PSS, the £fmax of electroluminescence was red-shifted. If the PEDOT:PSS film thicknesses were similar, the EL spectra were almost the same, independent of device processing scheme. The injection current and EL intensity were enhanced by doping PC61BM or MWCNT- C18. The electric conductivity parallel to film surface (£m¡ü) was increased as the doping concentration increased. Because of the extremely different aspect ratio, the MWCNT-C18 had a lower percolation threshold concentration. Therefore, at a low MWCNT-C18 doping concentration, the injection current and the EL intensity were enhanced compared with those of PC61BM.

The focus of this study is mono-layer polymer light emitting diode (PLED). The emitting layer is poly-p-phenylenebenzobisoxazole (PBO). PBO is a fully conjugated heterocyclic aromatic rigid-rod polymer. Anode is indium-tin-oxide (ITO). Cathode is aluminum (Al). We used UV epoxy resin to package PLED devices, then measured current-voltage response, electroluminescence (EL) emission, and device lifetime. We demonstrate that the packaged mono-layer PBO LED reduced its demise from water and oxygen. Device lifetime increased from 1 hour to several hundred hours. At a larger bias voltage or current, emission intensity and device efficiency became higher. But decay rate increased leading to shortened device lifetime. Device temperature appeared linearly with current density. A red shift of the EL emission was observed. The £fmax. of emission spectra moved from 534 nm (initial) to 582 nm (after 100 hrs). After thermal annealing at 120¢J for ten hours, threshold voltage increased from 5 V to 12 V, current density decreased to several 10 mA/cm2, luminous intensity improved several ten times to 10-2 cd/m2, emission color changed from yellow-green to orange, luminous efficiency improved from 10-7 to 10-4 cd/A, but device lifetime declined to less than 20 hrs.

Polymer photovoltaic cell (PV cell) utilizes a polymer to absorb photons for generating excitons. When excitons are separated into electrons and holes, the device has the photovoltaic effect. Polymer light emitting diode (PLED) injects electrons and holes respectively from cathode and anode into a polymer emission layer. Some of the electrons and the holes would recombine to induce light emission. This research used a heterocyclic aromatic rigid-rod polymer poly-p-phenylene- benzobisoxazole (PBO) as the opto-electronic layer, and a conducting material of poly(3,4-ethylenedioxythiophene):poly(4-styrenesulfonic acid) (PEDOT:PSS) as the hole transport layer. PV cells were fabricated using indium-tin-oxide (ITO) as anode and aluminium as cathode. Same layer arrangement was applied for PLEDs. These two kinds of devices were measured for electrical and optical response. It was evidenced that the addition of PEDOT:PSS layer facilitated the separation of excitons into electrons and holes at the PBO/PEDOT:PSS interface. Insertion of a LiF layer between PBO layer and Al cathode reduced their energy band gap and facilitated charge transport leading to an enhanced efficiency for PV cells and PLEDs. Thickness variations were found on spun PBO layer. According to emission intensity, we knew that the PBO layer quality was significant for electroluminescence. Introduction of a PEDOT:PSS layer improved the interface between ITO and PBO. The thickness of PEDOT:PSS layer depended on the ITO surface roughness. With a PEDOT:PSS layer, the opto-electronic efficiency of PV cell and PLED was improved.

Poly-p-phenylenebenzobisoxazole (PBO) and carbon nanotube (CNT) contain fully conjugated rod like backbone entailing excellent mechanical properties, thermo -oxidative stability and solvent resistance. Rigid-rod PBO is commonly processed by dissolving in methanesulfonic acid or Lewis acid. A CNT of multi-wall carbon nanotube (MWNT) was dissolved in a Lewis acid solution of PBO for dispersion, and then spun for thin film. MWNT concentration in the films was from zero up to 5 wt. %. Compared to that of pure PBO film, all PBO/MWNT composite films retained same but enhanced UV-Vis absorption peaks, according to MWNT concentration, showing that PBO and MWNT did not have overlapping electron orbitals affecting their energy gaps. The composite films were excited at 325 nm using a He-Cd laser for photoluminescence (PL) emission. All PL spectra had maximum intensity at 540 nm indicative of yellow-green light emission. The composite films were fabricated as light emitting diodes using indium-tin-oxide/glass as substrate and anode, as well as vacuum evaporated Al as cathode for respectively hole and electron injectors. In these light emitting devices, MWNT doped PBO would decrease threshold voltage for about 2 V. Up to 0.1 wt. % of MWNT, the device emission current was increased two orders of magnitude than those of the devices without MWNT. Further increase of MWNT caused a successive decrease in electroluminescence emission intensity attributed to a quench effect from aggregations of MWNTs. UV epoxy resin was applied to package the mono-layer and bilayer PBO light emitting devices. The UV epoxy resin had some gas release during encapsulation. The devices were packaged with vacuum and without vacuum encapsulation. It was demonstrated that the device encapsulation reduced its demise from water and oxygen. The vacuum encapsulation could remove gaseous volatile of the device to inhibit oxygen and moisture to prolong device lifetime. The main degradation of light emitting device was the oxidization of cathode. The interactions between nitrogen of PBO and H2O caused the formation of hydrogen bonding at room temperature. Oxygen and moisture diffused into PBO polymer and were suspected to form mid-gap state for the polymer. The mid energy band disappeared upon heat treatment before encapsulation. A device under a higher bias voltage was found to have a shorter lifetime, but a larger EL emission intensity. The EL emission intensity was not a constant under a constant current bias. The vacuum encapsulated device had two or twenty times lifetime than, respectively, the device encapsulation without vacuum evacuation or in ambient conditions. The sandwich structure of ITO/PBO/Al had no observable photovoltaic effect due to insufficient exciton separation into electrons and holes. Poly(2,3-dihydro thieno-1,4-dioxin):polystyrenesulfonate (PEDOT:PSS), a hole transferring medium, was spun into a thin-film between PBO and indium-tin-oxide to facilitate photovoltaic (PV) effect by forming a donor-acceptor interlayer to separate and to transport photoinduced charges. Optimum PBO thickness for the PV heterojunctions was about 71 nm at which the hole transferring PEDOT:PSS generated the maximum short circuit current (Isc) at a thickness of 115 nm. By using a layer of lithium fluoride (LiF) as an electron transferring layer adhering to Al cathode, the most open circuit voltage (Voc) and the maximum short circuit current (Isc) were achieved with a LiF thickness of 1-2 nm due to possible electric dipole effect leading to an increase of Voc from 0.7 V to 0.92 V and of Isc from about 0.1

Molecular light emitting diode, including organic light emitting diode (OLED) and polymer light emitting diode (PLED), is commonly consist of one or several molecular layer(s) sandwiched between an anode and a cathode. When electrons and holes are injected respectively from cathode and anode into the molecular layer by a bias voltage, these two types of carriers migrate towards each other and a fraction of them recombine to form light emission. The focus of this study is electrode modifications of molecular light emitting diode. The electrode modifications include using a low work function cathode material, a high work function anode material or inserting a very thin electrode modifier between molecular layer and electrode for enhancing the electron or the hole injection efficiency leading to higher electroluminescence emission and/or lower threshold voltage. Low work function metal, Mg, could effectively reduce the electron injection barrier between molecular layer and cathode leading to better emission brightness and threshold voltage. A monolayer rigid-rod poly-p-phenylenebenzobisthiazole (PBT) or poly-p-phenylenebenzobis- oxazole (PBO) PLED with Mg cathode demonstrated a low threshold voltage of 3 V. Besides, a very thin layer of LiF (or Al2O3) inserted between molecular layer and Al cathode was applied to enhance the electron injection efficiency leading to a stronger electroluminescence intensity and a low threshold voltage of 2.8 V. On anode modification, a thin PBO layer was inserted between molecular layer and the indium-tin-oxide (ITO) substrate for improving the electroluminescence emission brightness and the threshold voltage. The PBO modified anode could effectively enhance the electro- luminescence intensity and lower the threshold voltage to 1 V~ 3 V on several mono- or multi-layer molecular light emitting diodes. Besides, a novel ITO substrate cleaning method via acid treatment was applied for increasing the work function of ITO to effectively enhance the hole injection efficiency.

A heterocyclic aromatic rigid-rod polymer poly-p-phenylene-benzobisoxazole (PBO) was applied as the opto-electronic layer¡Fand a conducting material of poly(3,4-ethylenedioxythio-phene):poly(4-styrenesulfonic acid) (PEDOT: PSS) was used as the hole transport layer. Aluminum (Al) and indium tin oxide (ITO) were served as device cathode and anode¡Arespectively, fabricated into a bi-layer structure of ITO/PEDOT:PSS/PBO/Al for electrical and luminescence responses. This research demonstrated an increase of current density and a decrease of threshold voltage with a decrease of PBO layer thickness from 90 nm to 27 nm to facilitate electron tunneling and electron-hole recombination. With a lower spin coating speed, polymer chain would aggregate and inter-penetrate resulted in red-shift of electroluminescence (EL) emission spectrum. Furthermore, micro-cavity effect might influence EL spectrum by varying layer thickness. Modulation of PBO layer thickness led to tunable EL emission color. It was also demonstrated that an increase of current density and a slightly decrease of threshold voltage with a PEDOT:PSS film thickness changing from 96 nm to 17 nm at a constant PBO layer thickness of 90 nm. Micro-cavity effect thus influenced EL emission for a tunable emission color. Photolithography was applied to obtain ITO substrate of grating depth of periodic variation and then coated with a PEDOT:PSS leading to a grated PEDOT:PSS layer of periodic thickness. This led to ITO/PEDOT:PSS/PBO/Al device showing broadened EL emission spectra.

No description available.

In this research, we investigated a novel rigid-rod polymer sPBI for mono-layer polymer light emitting diode (PLED) fabrication and luminescence emission. sPBI could be a luminescent polymer with a low threshold voltage of 4.5 V and green light electroluminescence emission (530 nm). Its SO3H pendant attached to the p-phenyl ring improved electronic delocalization along the backbone resulted in a red shift of the absorption spectrum. By attaching propanesulfonated pendants to the heterocyclic moiety of intractable fully conjugated sPBI, water-soluble rigid-rod polyelectrolyte sPBI-PS(Li+) was synthesized to promote its processibility in water or common organic solvent. This water-soluble rigid-rod polyelectrolyte sPBI-PS(Li+) was fabricated for polymer light-emitting electrochemical cells (PLECs) with LiCF3SO3 (LiTf) or LiN(CF3SO2)2 (LiTfSI) dopants for investigating the influence of propanesulfonated pendants as well as dopants on the opto-electronic emission and the room-temperature DC conductivity. The effect of lithium salts (LiTf or LiTfSI) on photoluminescence color of doped sPBI-PS(Li+) films was negligible. sPBI-PS(Li+) PLECs doped with 0.41 and 1.01 wt. % of LiTfSI showed higher green light electroluminescence emission (514 nm) with a lower threshold voltage of 3.0 V and -4.6 V, respectively. Emission brightness of the sPBI-PS(Li+) PLEC did not raise upon increasing the ionic conductivity of the luminescent layer.

In this thesis, we investigated several photoelectric material systems consisted of conjugated polymers by means of computer simulation. We combined several theory and simulation methods to meodeling different subjects from atomic to mesoscopic scale. We dealt with the problems such as quantum efficiency, structure characteristic, and the phase behavior in material. We hope to have better understanding of the relationship between structure characteristic and functional property in material. It will help an engineering designer to adjust the variables that optimize characteristics linking the synthesis of advanced materials with desired physical properties. This work can be divided into three parts. Long side chain substituted PPV polymers applied in light-emitting diode material : Molecular dynamics simulations were employed to investigate structure features and segment orientation of four poly(phenylene vinylene) (PPV)-like conjugated polymers with long flexible side chains at room temperature. In the simulations, the main chains of the polymers were found to be semi-rigid and to exhibit a tendency to coil into ellipsoidal helices or form zigzag conformations of only limited regularity. It was shown that continuous segments of a chain which are quasi-coplanar along the backbone are in a range of 2~4 repeat units. This implies that long-range electron transfer along same backbones of these polymers may not happen but may be mediated by interchain interactions. The ordered orientation and coupling distance of interchain aromatic rings are found to correlate with important optical properties of materials. Then we combined molecular dynamics simulation and density matrix methods modeling of amorphous light-emitting polymers. A simplified method combining molecular dynamics (MD) simulation and density matrix (DM) theory was developed for the prediction of optical properties of long side chain substituted poly(phenylene vinylene) (PPV) polymers. This MD+DM method takes account of the complexity of molecular packing of polymer chains. The method has been tested to simulate the absorption spectra of four model systems. The wavelengths of absorption maxima of the calculated spectra of these four conjugated polymers are in reasonable agreement with experimental data. The simulation also demonstrated that the importance of including interchain interactions in the calculation. Ion-conducting polymer sPBI-PS(Li+): To understand the mechanism of ionic migration in the amorphous matrixes of polymer electrolytes is crucial for their applications in modern technologies. Here, molecular dynamics (MD) simulation was carried out to investigate the ionic conduction mechanism of a particular conjugated rigid-rod polymer, sPBI-PS(Li+). The backbone of this polymer is poly[(1, 7- dihydrobenzo[1, 2-d:4,5-d¡¦]diimidazole- 2,6-diyl)-2-(2-sulfo)-p-phenylene]. The polymer has pendants of propane sulfonate Li+ ionomer. The MD simulations showed that the main chains of sPBI-PS(Li+) are in layer-like structure. The further detailed structure analysis suggested that the £k-electron of this polymer is not delocalized among aromatic rings. This agrees with the experimental result that sPBI-PS(Li+) shows no electronic conductivity and the conductivity of this polymer is mainly ionic. The calculated migration channels of lithium ions and electrostatic potential distributions indicated clearly that the polymer matrix is anisotropic for the migrations of ions. The migration of lithium ions along the longitudinal direction is more preferable than that along the transverse direction. The relaxations of the polymer host were found to play important roles in the transfer process of lithium ions. The hopping of lithium ion from one -SO3-1 group to another is correlated strongly with characteristic motions of -SO3-1 group on a time scale of about 10-13 s. Self-assembly functional material. Dissipative particle dynamics (DPD) simulations were carried out to investigate mixed ionic and non-ionic molecules, sodium tetradecyl sulfate (STS) and tetradecyl triethoxylated ether (C14E3) aqueous system. Different types of mixed micelles are formed depending on the concentrations of STS and C14E3. Our results are in good agreement to the early NMR measurements. From the investigation of surfactant aggregation, we understand the self-assembly mechanism and classical phase behavior in general diblock copolymer. Further, we investigated the self-assembly process on a particular mushroom-shaped supramolecular film material from molecular character to phase behavior. The miniaturized rod-coil triblock copolymers (PS-PI-RCBC) HEMME had been found to self-assemble into well-ordered nanostructures and unusual head to tail multilayer structure. The purpose of our study is to obtain fundamental understanding the connection of the inherent morphological characterization of single molecule and the mechanism of phase behavior of this polar self-assembly system. Dissipative particle dynamics simulation was carried out to study the mechanism of phase behavior of the solvent-copolymers system. We found that the solvent-induced polar effect under different temperature is important in the process of self-assembly of block copolymers. In different temperature the solvent induces hybrid structure aggregation. Our results are consistent with experimental observations and give evidence for a special mechanism governing the unusual phase behavior in thin films of modulated phases. The sizes and stabilization energies of mushroom-shaped supramolecular clusters were predicted by molecular modeling method. Clusters of sizes from 16 to 90 molecules were found to be stable. In combination of classical and simple quantum mechanical calculations, the band gaps of HEMME clusters with various sizes were estimated. The band gap was converged at 2.45 eV for cluster contains 90 molecules. Nonlinear optical properties of the material were investigated by the semi-empirical quantum mechanical calculations of molecular dipole moment and hyperpolarizabilities. Significant second-order nonlinear optical properties were shown from these calculated properties.