We report electroabsorption measurements of polymer light-emitting diodes, (LEDs), fabricated with poly(4-4′-diphenylene diphenylvinylene), PDPV, as the emissive layer, Ca–Al cathodes, and indium tin oxide (ITO) anodes, with and without a doped conducting polymer hole injection/transport layer, namely poly(3,4-ethylene dioxythiophene), PEDOT, doped with poly(styrene sulfonate), PSS−. In these structures, the bias at which the electroabsorption signal is null corresponds to the difference between the electrodes’ work functions. We find that such a built-in voltage increases by 0.5 V when a PEDOT:PSS film is incorporated between the ITO electrode and the emissive layer. This leads to a marked reduction of the anode barrier height at the hole-injecting interface, and accounts for a variety of improvements brought about by the PEDOT insertion, namely: (a) the increase of luminescence efficiency, (b) the reduction of the turn-on voltage, and (c) the increase of the device lifetime.

We report combined studies of the influence of chemical and physical treatments on the properties of indium–tin oxide (ITO) thin films. The ITO films were also used as transparent anodes of polymeric light-emitting diodes (LEDs) incorporating poly(p-phenylene vinylene) (PPV) as the emitter material, with, or without, doped poly(3,4-ethylene dioxythiophene) (PEDOT) as a hole-injection/transport layer. Structures based on a soluble green derivative of PPV, poly(4,4′-diphenylene diphenylvinylene) were also tested. We studied chemical (aquaregia, degreasing, RCA protocol) and physical (oxygen and argon plasmas, Teflon, and paper rubbing) treatments and, in contrast to recently published work, we find that for Balzer Baltracon ITO, oxygen plasma and not aquaregia yields the highest efficiencies and luminances and the lowest drive voltages. For oxygen-plasma-treated anodes, the device efficiency clearly correlates with the value of the ITO surface work function, which in turn depends on the time of treatment. Interestingly, we find that work-function variations induced by our oxygen-plasma treatment are unchanged after long-term storage in air and in the dark. Unexpectedly, we also find that devices incorporating a PEDOT layer benefit from an appropriate treatment of the ITO surface, for both efficiency and lifetime. The results shed light on the physics of conjugated, organic semiconductors and related devices, and in particular on the presence and the role of an anodic energy barrier on the LEDs mechanism of operation. We also discuss the implications of our integrated experimental study in relation to the modification of the ITO sheet resistance, surface and bulk composition, and surface morphology.

Recent progress in the synthesis and characterization of well-defined conjugated polymers and oligomers is presented. The different synthetic schemes for most of the important conjugated polymers will be discussed using a subdivision into three main sections, covering hydrocarbon polymers, heterocyclic polymers and the oligomers, respectively. Although the materials properties will be referred to, the main emphasis of the review is directed to the different strategies that are now available to produce conjugated polymers and welldefined oligomers in a reproducible way and with full control over most of the important macromolecular properties.

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The self-assembly of alpha,alpha'-linked sexithiophenes with chiral and achiral penta(ethylene glycol) chains attached at the alpha-positions of the terminal rings, that is, 2,2':5',2'':5'',2''':5''',2'''':5'''',2'''''-sexithiophene-5,5'''''-dicarboxylic acid-2S)-2-methyl-3,6,9,12,15-pentaoxahexadecyl ester (1) and 2,2':5',2'':5'',2''':5'''',2''''':5''''',2'''''-sexithiophene-5,5'''''-dicarboxylic acid-3,6,9,12,15-pentaoxahexadecyl ester (2), respectively is described. Analysis of the UV/vis, fluorescence, circular dichroism, and circular polarization of luminescence spectroscopic data shows that these compounds form chiral aggregates in polar solvents and in the solid state. In n-butanol aggregation occurs at temperatures below 30 degrees C, while above this threshold temperature the aggregates break up without an intermediate disordered state of aggregation, and the compounds are molecularly dissolved. The "melting temperature" of the aggregates depends on the concentration of sexithiophene, indicating that the optical changes observed are a result of intermolecular processes. Mass spectrometric measurements reveal that 1 and 2 can form mixed aggregates. Analysis of the optical spectra reveals that in these mixed aggregates, chiral 1 molecules act as "sergeants" to direct the packing of the "soldiers" 2, illustrating cooperativity within the columns. In water, the same type of chiral aggregates are formed as in n-butanol below 30 degrees C; however, these aggregates are still present, but the chirality is lost above 30 degrees C. In spin-coated films of 1 chiral aggregates are present. AFM studies show that 1 self-organizes into chiral fiberlike structures in the solid state. Furthermore both 1 and 2 display thermotropic liquid crystalline behavior between 180 and 200 degrees C.