Research in the use of organic polymers as the active semiconductors in light-emitting diodes has advanced rapidly, and prototype devices now meet realistic specifications for applications. These achievements have provided insight into many aspects of the background science, from design and synthesis of materials, through materials fabrication issues, to the semiconductor physics of these polymers.

Electroluminescence in conjugated polymers

A review was presented to demonstrate a historical description of the synthesis of light-emitting conjugated polymers for applications in electroluminescent devices. Electroluminescence (EL) was first reported in poly(para-phenylene vinylene) (PPV) in 1990 and researchers continued to make significant efforts to develop conjugated materials as the active units in light-emitting devices (LED) to be used in display applications. Conjugated oligomers were used as luminescent materials and as models for conjugated polymers in the review. Oligomers were used to demonstrate a structure and property relationship to determine a key polymer property or to demonstrate a technique that was to be applied to polymers. The review focused on demonstrating the way polymer structures were made and the way their properties were controlled by intelligent and rational and synthetic design.

Synthesis of Light-Emitting Conjugated Polymers for Applications in Electroluminescent Devices

4. Survey of Novel Multiphoton Active Materials 1257 4.1. Multiphoton Absorbing Systems 1257 4.2. Organic Molecules 1257 4.3. Organic Liquids and Liquid Crystals 1259 4.4. Conjugated Polymers 1259 4.4.1. Polydiacetylenes 1261 4.4.2. Polyphenylenevinylenes (PPVs) 1261 4.4.3. Polythiophenes 1263 4.4.4. Other Conjugated Polymers 1265 4.4.5. Dendrimers 1265 4.4.6. Hyperbranched Polymers 1267 4.5. Fullerenes 1267 4.6. Coordination and Organometallic Compounds 1271 4.6.1. Metal Dithiolenes 1271 4.6.2. Pyridine-Based Multidentate Ligands 1272 4.6.3. Other Transition-Metal Complexes 1273 4.6.4. Lanthanide Complexes 1275 4.6.5. Ferrocene Derivatives 1275 4.6.6. Alkynylruthenium Complexes 1279 4.6.7. Platinum Acetylides 1279 4.7. Porphyrins and Metallophophyrins 1279 4.8. Nanoparticles 1281 4.9. Biomolecules and Derivatives 1282 5. Nonlinear Optical Characterizations of Multiphoton Active Materials 1282

Multiphoton Absorbing Materials : Molecular Designs, Characterizations, and Applications

CONJUGATED polymers have been incorporated as active materials into several kinds of electronic device, such as diodes, transistors1 and light-emitting diodes2. The first polymer light-emitting diodes were based on poly(p-phenylene vinylene) (PPV), which is robust and has a readily processible precursor polymer. Electroluminescence in this material is achieved by injection of electrons into the conduction band and holes into the valence band, which capture one another with emission of visible radiation. Efficient injection of electrons has previously required the use of metal electrodes with low work functions, primarily calcium; but this reactive metal presents problems for device stability. Here we report the fabrication of electroluminescent devices using a new family of processible poly(cyanoterephthalylidene)s. As the lowest unoccupied orbitals of these polymers (from which the conduction band is formed) lie at lower energies than those of PPV, electrodes made from stable metals such as aluminium can be used for electron injection. For hole injection, we use indium tin oxide coated with a PPV layer; this helps to localize charge at the interface between the PPV and the new polymer, increasing the efficiency of recombination. In this way, we are able to achieve high internal efficiencies (photons emitted per electrons injected) of up to 4% in these devices.

Efficient light-emitting diodes based on polymers with high electron affinities

The design and characterization of metal–organic complexes for optoelectronic applications is an active area of research. The metal–organic complex offers unique optical and electronic properties arising from the interplay between the inorganic metal and the organic ligand. The ability to modify chemical structure through control over metal–ligand interaction on a molecular level could directly impact the properties of the complex. When deposited in thin film form, this class of materials enable the fabrication of a wide variety of low-cost electronic and optoelectronic devices. These include light emitting diodes, solar cells, photodetectors, field-effect transistors as well as chemical and biological sensors. Here we present an overview of recent development in metal–organic complexes with controlled molecular structures and tunable properties. Advances in extending the control of molecular structures to solid materials for energy conversion and information technology applications will be highlighted.

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Recent progress in metal–organic complexes for optoelectronic applications

The authors report a study of the photophysical properties of poly(p-phenylene vinylene), PPV, prepared in a way that gives an especially high degree of intrachain order. Optical absorption, photoluminescence, photoinduced absorption, and photoconductivity excitation spectra are presented and compared to data reported for less well ordered PPV. Spectral red shifts, sharpening of spectral lines, and a transfer of oscillator strength into the vibronic ground states of the electronic transitions are observed. Photoinduced absorption due to long-lived charged excitations, previously reported for less ordered PPV, could not be detected in this material. Photoconductivity excitation spectra show a steep rise at the absorption edge with no appreciable offset between the onsets for photoconduction and absorption. A very slow photocurrent component is observed, which the authors associated with the trapping and subsequent thermal release of photocarriers.

http://iopscience.iop.org/article/10.1088/0953-8984/5/38/011/pdf

Optical spectroscopy of highly ordered poly(p-phenylene vinylene)

Low-temperature site-selective fluorescence (SSF) spectroscopy is employed to study morphological effects on the conformation of poly(p-phenylene vinylene) (PPV) and its phenyl-substituted, soluble derivative poly(phenylphenylenevinylene) (PPPV). Samples of PPV prepared as spin-coated thin films and stretch-aligned free-standing films, and samples of PPPV prepared as cast films and as blends with poly(methylmethacrylate) and polycarbonate have been studied. The results that the authors present are considered with the notion that each polymer sample consists of an array of ordered chain segments whose average length reflects the perfection of the local structure. The statistical distribution of the segment lengths is responsible for inhomogeneous broadening of the optical spectra (absorption and emission). The dominant electronic excitation created by photoexcitation across the pi - pi * energy gap is a singlet exciton that can execute a random walk among the chain segments. SSF spectroscopy allows the authors to distinguish the contributions to the apparent fluorescence Stokes shift that arise from energy relaxation through excitation migration (spectral diffusion) and from structural relaxation of the polymer chain (self-localization). The structural contribution to the Stokes shift approaches zero in well aligned PPV and reaches values of up to 500 cm-1 in highly disordered PPPV films. The SSF method also provides a means of assessing the extent of phase separation that occurs in PPPV blends.

Conformational effects in poly(p-phenylene vinylene)s revealed by low-temperature site-selective fluorescence

Several precursor polymer routes to poly(p-phenylenevinylene)4, poly[(2,5-dimethyl-p-phenylene)vinylene]10 and poly[(2,5-dimethoxy-p-phenylene)vinylene]15 are described. Base induced polymerisation of bis-sulfonium salt monomers afforded the polyelectrolytes 3 and 9 which were converted respectively directly into either polymer 4 or 10. Optimised conditions for the complete displacement of sulfonium groups by methanol to produce the corresponding methoxy precursor polymers 5, 11 and 17 are reported. The fully conjugated polymers obtained after heat and acid treatment of these precursors have been characterised and compared with those obtained via different precursor routes. The 1H NMR spectra of the precursor polymers, as well as IR and UV–VIS data of both the precursor polymers and the materials obtained after conversion into the poly(arylenevinylene)s are discussed.

Precursor route chemistry and electronic properties of poly(p-phenylenevinylene), poly[(2,5-dimethyl-p-phenylene)vinylene] and poly[(2,5-dimethoxy-p-phenylene)vinylene]

Photoluminescence and electroluminescence in conjugated polymeric systems

Conjugated polymers such as poly(p-phenylenevinylene), (PPV, see Figure), show real promise in optoelectronic applications A new synthetic route to improved PPV is presented, involving the thermal conversion of a precursor polymer containing rigid rod conjugated segments joined by flexible spacer groups A high degree of interchain ordering results which influences the optical response of the material

D. A. Halliday

Papers

Optical spectroscopy of highly ordered poly(p-phenylene vinylene)

Conformational effects in poly(p-phenylene vinylene)s revealed by low-temperature site-selective fluorescence

Precursor route chemistry and electronic properties of poly(p-phenylenevinylene), poly[(2,5-dimethyl-p-phenylene)vinylene] and poly[(2,5-dimethoxy-p-phenylene)vinylene]

Photoluminescence and electroluminescence in conjugated polymeric systems

Large changes in optical response through chemical pre‐ordering of poly(p‐phenylenevinylene)