Organic light emitting diodes with europium (III) emissive layers based on beta-diketonate complexes: The influence of the central ligand

This work shows a comparative study of organic light emitting diodes based on four different europium complexes with the general formula, Eu(CLs)(3)bipyridine, where the central ligands are DBM [tris(dibenzoylmethane)], TTA [tris(1-(2-thieneyl)-4,4,4-trifluoro-1,3-butanedione)], NTA [tris(1-(2-naphthoyl)-3,3,3-trifluoroacetone)] and BTA [tris(1-(2-benzoyl)-3,3,3-trifluoroacetone)]. All devices have a driving voltage of 14-16 V, a very low electrical current at normal operation (less than 1 mA) and a good Wall Plug Efficiency (up to near 10(-3)%). The most suitable central ligand was found to be DBM, with an optical power up to 200 nW (at 612 nm). The BTA exhibits the lowest stability under high applied voltages. The other central ligands have similar results among them. The electroluminescence spectra clearly show the europium ion transitions (with a strong (5)D(0) -> (7)F(2) line) with a CIE color coordinate around (0.56, 0.34). (C) 2008 Elsevier B.V. All rights reserved.

Photo and electroluminescence behavior of Tb(ACAC)(3)phen complex used as emissive layer on organic light emitting diodes

This work shows the luminescence properties of a rare-earth organic complex, the Tb(ACAC)(3)phen. The results show the (5)D(4)->(7)F(3,4,5,6) transitions with no influence of the ligand. The photoluminescence excitation spectrum is tentatively interpreted by the ligands absorption. An organic light emitting diode (CLED) was made by thermal evaporation using TPD (N,N`-bis(3-methylphenyl)N,N`-diphenylbenzidine) and Alq3 (aluminum-tris(8-hydroxyquinoline)) as hole and electron transport layers, respectively. The emission reproduces the photoluminescence spectrum of the terbium complex at room temperature, with Commission Internationale de l`Eclairage - CIE (x,y) color coordinates of (0.28,0.55). No presence of any bands from the ligands was observed. The potential use of this compound in efficient devices is discussed. (C) 2008 Elsevier B.V. All rights reserved.

Influence of polyaniline and phthalocyanine hole-transport layers on the electrical performance of light-emitting diodes using MEH-PPV as emissive material

The influence of layer-by-layer films of polyaniline and Ni-tetrasulfonated phthalocyanine (PANI/Ni-TS-Pc) on the electrical performance of polymeric light-emitting diodes (PLED) made from (poly[2-methoxy-5-(2`-ethyl-hexyloxy)-1,4-phenylene vinylene]) (MEH-PPV) is investigated by using current versus voltage measurements and impedance spectroscopy. The PLED is composed by a thin layer of MEH-PPV sandwiched between indium tin oxide (ITO) and aluminum electrodes, resulting in the device structure ITO/(PANI/Ni-TS-Pc)(n)/MEH-PPV/Al, where n stands for the number of PANI/Ni-TS-Pc bilayers. The deposition of PANI/Ni-TS-Pc leads to a decrease in the driving voltage of the PLEDs, which reaches a minimum when n = 5 bilayers. In addition, impedance spectroscopy data reveal that the PLED impedance decreases as more PANI/Ni-TS-Pc bilayers are deposited. The PLED structure is further described by an equivalent circuit composed by two R-C combinations, one for the bulk and other for the interface components, in series with a resistance originated in the ITO contact. From the impedance curves, the values for each circuit element is determined and it is found that both, bulk and interface resistances are decreased upon PANI/Ni-TS-Pc deposition. The results indicate that PANI/NiTS-Pc films reduce the contact resistance at ITO/MEH-PPV interface, and for that reason improve the hole-injection within the PLED structure. (c) 2007 Elsevier B.V. All rights reserved.

Development and characterization of light-emitting diodes (LEDs) based on ruthenium complex single layer for transparent displays

In this work, two ruthenium complexes, [Ru(bpy)(3)](PF6)(2) and [Ru(ph2phcn)(3)](PF6)(2) in poly(inethylinethacrylate) matrix were employed to build single-layer light-emitting electrochemical cells by spin coating on indium tin oxide substrate. In both cases the electroluminescence spectra exhibit a relatively broad band with maxima near to 625 rim and CIE (x, y) color coordinates of (0.64, 0.36), which are comparable with the photoluminescence data in the same medium. The best result was obtained with the [Ru(bpy)(3)](PF6)(2) device where the optical output power approaches 10 mu W at the band maximum with a wall-plug efficiency higher than 0.03%. The lowest driving voltage is about 4 V for an electrical current of 20 mA. (c) 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Correlation Between Molecular Conformation, Packing, and Dynamics in Oligofluorenes: A Theoretical/Experimental Study

Fluorene-based systems have shown great potential as components in organic electronics and optoelectronics (organic photovoltaics, OPVs, organic light emitting diodes, OLEDs, and organic transistors, OTFTs). These systems have drawn attention primarily because they exhibit strong blue emission associated with relatively good thermal stability. It is well-known that the electronic properties of polymers are directly related to the molecular conformations and chain packing of polymers. Here, we used three oligofluorenes (trimer, pentamer, and heptamer) as model systems to theoretically investigate the conformational properties of fluorene molecules, starting with the identification of preferred conformations. The hybrid exchange correlation functional, OPBE, and ZINDO/S-CI showed that each oligomer exhibits a tendency to adopt a specific chain arrangement, which could be distinguished by comparing their UV/vis electronic absorption and C-13 NMR spectra. This feature was used to identify the preferred conformation of the oligomer chains in chloroform-cast films by comparing experimental and theoretical UV/vis and C-13 NMR spectra. Moreover, the oligomer chain packing and dynamics in the films were studied by DSC and several solid state NMR techniques, which indicated that the phase behavior of the films may be influenced by the tendency that each oligomeric chain has to adopt a given conformation.

Langmuir and Langmuir-Blodgett films of a quinoline-fluorene based copolymer

The fabrication of Langmuir-Blodgett (LB) films of synthetic polymers allows the control of molecular architecture in order to optimize physical properties. In this paper, the surface chemistry of a quinoline-fluorene based copolymer spread on the air-water interface is investigated. Surface pressure-area isotherms as well as Polarization-Modulation Infrared Reflection-Absorption Spectroscopy (PM-IRRAS) were employed to characterize the films, which could be transferred to solid supports by the LB technique. Atomic force microscopy as well as UV-Vis and fluorescence spectroscopies have shown a regular deposition of the polymers, and the luminescence properties could be controlled with the number of layers deposited on the solid support. As a result, the photoluminescence of the LB films was considerably higher than that observed for the spin coated film, and the maximum emission peak was shifted to higher energies, which is attributed to the molecular-level interactions within the layer-ordered structure of the LB film. The luminescence response would possibly be tuned to approach the highest level, which allows the films to be employed in future applications in efficient optical devices such as organic light-emitting diodes (OLEDs). (C) 2011 Elsevier B.V. All rights reserved.

Luminous efficiency enhancement of PVK based OLEDs with fac-[ClRe(CO)(3)(bpy)]

The luminous efficiency of organic light-emitting diodes based on poly(N-vinylcarbazole), PVK, was improved by adding fac-[ClRe(CO)(3)(bpy)], bpy = 2,2`-bipyridine, to PVK host. Emissive layers with various Re(I) complex/host ratio were employed and optoelectronic properties were compared with the single PVK device. The single PVK device exhibits a characteristic electroluminescence with blue emission, lambda(max) 420 nm, assigned to the PVK excimer. On the other hand, the intense and broad band at lambda(max) 580 nm of the Re(I) complex/PVK OLEDs is ascribed to the metal-to-ligand charge transfer excited state emission of fac-[ClRe(CO)(3)(bpy)]. At 30 V, the device luminous efficiency increased from 16 mcd/A for the single PVK device to 211 mcd/A for the 11% (w/w) Re(I) complex/PVK OLED, in which fac-[ClRe(CO)(3)(bpy)] acts as an electron-trap in PVK films. The device current is space-charge limited and exhibits typical emissive layer thickness dependence. (C) 2011 Elsevier B.V. All rights reserved.

Transient and d.c. analysis of the operation mechanism of light-emitting electrochemical cells

Light-emitting electrochemical cells (LECs) made of electroluminescent polymers were studied by d.c. and transient current-voltage and luminance-voltage measurements to elucidate the operation mechanisms of this kind of device. The time and external voltage necessary to form electrical double layers (EDLs) at the electrode interfaces could be determined from the results. In the low-and intermediate-voltage ranges (below 1.1 V), the ionic transport and the electronic diffusion dominate the current, being the device operation better described by an electrodynamic model. For higher voltages, electrochemical doping occurs, giving rise to the formation of a p-i-n junction, according to an electrochemical doping model. Copyright (C) EPLA, 2012

Polymer Light Emitting Diode Using PFT-Poly(9,9 `-n-dihexil-2,7-fluorenodiilvinylene-alt-2,5thiophene)

The development of new electroluminescence polymers for specific colour tuning in Polymer Light Emitting Devices (PLEDs) is currently one of the most important fields for organic electronics. This work reports a synthesis of a new electroluminescent polymer and the concomitant test as PLED emissive layer. The polymer, synthesised from fluorene, is poly(9,9`-n-dihexil-2,7-fluorenodiilvinylene-alt-2,5thiophene) or PFT The luminescence shows large bands with maxima around 480 nm in absorption and 560 nm in emission. The device was made in a three layer structure, with PEDOT:PSS as hole transport layer, PFT as emissive layer and butyl-PBD as electron transport layer. The electroluminescence spectrum shows a strong band peaked at 540 nm. For an applied voltage of 12 Volt, the brightness at normal angle of viewing is near 10 cd/m(2) and the luminous efficiency is of 0.01 lm/W. A discussion about carrier transport and the electroluminescence properties is made.

Electroluminescence and electric current response spectroscopy applied to the characterization of polymer light-emitting electrochemical cells

Frequency-dependent electroluminescence and electric current response spectroscopy were applied to polymeric light-emitting electrochemical cells in order to obtain information about the operation mechanism regimes of such devices. Three clearly distinct frequency regimes could be identified: a dielectric regime at high frequencies; an ionic transport regime, characterized by ionic drift and electronic diffusion; and an electrolytic regime, characterized by electronic injection from the electrodes and electrochemical doping of the conjugated polymer. From the analysis of the results, it was possible to evaluate parameters like the diffusion speed of electronic charge carriers in the active layer and the voltage drop necessary for operation. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.4752438]

Photophysical properties of a fluorene-bipyridine copolymer and its complexes with europium

The synthesis and structural characterization of a europium complexed fluorene-bipyridine copolymer are described. A level of ion insertion of 80% in molar basis was achieved, and theoretical calculations showed that it required a twist of 179 degrees (49 kJ) between the pyridine units. Spectroscopy data showed that no electronic coupling between the main backbone and the complexation sites had occurred, but these hindered the interchain aggregation observed in the non complexed polymer. Preliminary electroluminescence studies showed that the EL and PL spectra are consistent, and that the ion had a trapping effect in the charge transport. (C) 2011 Elsevier B.V. All rights reserved.

Determination of carrier mobility in MEH-PPV thin-films by stationary and transient current techniques

Charge transport and shelf-degradation of MEH-PPV thin-films were investigated through stationary (e.g. current versus voltage - JxV) and transient (e.g. Time-of-Flight - ToF, Dark-Injection Space-Charge-Limited Current - DI-SCLC, Charge Extraction by Linearly Increasing Voltage - CELN) current techniques. Charge carrier mobility in nanometric films was best characterized through JxV and DI-SCLC. It approaches 10(-6) cm(2)Ns under a SCLC regime with deep traps for light-emitting diode applications. ToF measurements performed on micrometric layers (i.e. - 3 mu m) confirmed studies in 100 nm-thick films as deposited in OLEDs. All results were comparable to a similar poly(para-phenylene vinylene) derivative, MDMO-PPV. Electrical properties extracted from thin-film transistors demonstrated mobility dependence on carrier concentration in the channel (similar to 10(-7)-10(-4) cm(2)/Vs). At low accumulated charge levels and reduced free carrier concentration, a perfect agreement to the previously cited techniques was observed. Degradation was verified through mobility reduction and changes in trap distribution of states. (C) 2011 Elsevier B.V. All rights reserved.

Effect of light sources and curing mode techniques on sorption, solubility and biaxial flexural strength of a composite resin

Adequate polymerization plays an important role on the longevity of the composite resin restorations. Objectives: The aim of this study was to evaluate the effect of light-curing units, curing mode techniques and storage media on sorption, solubility and biaxial flexural strength (BFS) of a composite resin. Material and Methods: Two hundred and forty specimens were made of one composite resin (Esthet-X) in a stainless steel mold (2 mm x 8 mm 0), and divided into 24 groups (n=10) established according to the 4 study factors: light-curing units: quartz tungsten halogen (QTH) lamp and light-emitting diodes (LED); energy densities: 16 J/cm(2) and 20 J/cm(2); curing modes: conventional (CM) and pulse-delay (PD); and permeants: deionized water and 75% ethanol for 28 days. Sorption and solubility tests were performed according to ISO 4049:2000 specifications. All specimens were then tested for BFS according to ASTM F394-78 specification. Data were analyzed by three-way ANOVA followed by Tukey, Kruskal-Wallis and Mann-Whitney tests (alpha=0.05). Results: In general, no significant differences were found regarding sorption, solubility or BFS means for the light-curing units and curing modes (p>0.05). Only LED unit using 16 J/cm(2) and PD using 10 s produced higher sorption and solubility values than QTH. Otherwise, using CM (16 J/cm(2)), LED produced lower values of BFS than QTH (p<0.05). 75% ethanol permeant produced higher values of sorption and solubility and lower values of BFS than water (p<0.05). Conclusion: Ethanol storage media produced more damage on composite resin than water. In general the LED and QTH curing units using 16 and 20 J/cm(2) by CM and PD curing modes produced no influence on the sorption, solubility or BFS of the tested resin.

Efficiency of extrinsic and intrinsic charge-carrier photogeneration processes obtained from the steady-state photocurrent action spectra of poly(p-phenylene vinylene) derivatives

The efficiency of the charge-carrier photogeneration processes in poly(2,5-bis(3',7'-dimethyl-octyloxy)-1,4-phenylene vinylene) (OC(1)OC10-PPV) has been analyzed by the spectral response of the photocurrent of devices in ITO/polymer/Al structures. The symbatic response of the photocurrent action spectra of the OC1OC10-PPV devices, obtained for light-excitation through the ITO electrode and for forward bias, has been fitted using a phenomenological model which considers that the predominant transport mechanism under external applied electric field is the drift of photogenerated charge-carriers, neglecting charge-carrier diffusion. The proposed model takes into account that charge-carrier photogeneration occurs via intermediate stages of bounded pairs (excitonic states), followed by dissociation processes. Such processes result in two different contributions to the photoconductivity: The first one, associated to direct creation of unbound polaron pairs due to intrinsic photoionization; and the second one is associated to secondary processes like extrinsic photoinjection at the metallic electrodes. The results obtained from the model have shown that the intrinsic component of the photoconductivity at higher excitation energies has a considerably higher efficiency than the extrinsic one, suggesting a dependence on the photon energy for the efficiency of the photogeneration process.

Electroluminescence of phenylene-vinylene random copolymers with different conjugation lengths

PPV random derivates were synthesized and characterized. Polymer light emitting diodes (PLEDs) were assembled using the random copolymers as emissive layer and showed EL in the blue-green region in function of the method of preparation. The increase in the average conjugation degree in the polymer chain led to the reduction of the turn-on voltage of the device. The addition of Alq3 as ETL increased tenfold the luminescence efficiency. (C) 2009 Elsevier B.V. All rights reserved.