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

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Electroluminescence of zinc oxide thin-films prepared via polymeric precursor and via sol-gel methods

Zinc oxide (ZnO) is an electroluminescent (EL) material that can emit light in different regions of electromagnetic spectrum when electrically excited. Since ZnO is chemically stable, inexpensive and environmentally friendly material, its EL property can be useful to construct solid-state lamps for illumination or as UV emitter. We present here two wet chemical methods to prepare ZnO thin-films: the Pechini method and the sol-gel method, with both methods resulting in crystalline and transparent films with transmittance > 85% at 550 nm. These films were used to make thin-film electroluminescent devices (TFELD) using two different insulator layers: lithium fluoride (LiF) or silica (SiO2). All the devices exhibit at least two wide emission bands in the visible range centered at 420 nm and at 380 nm attributed to the electronic defects in the ZnO optical band gap. Besides these two bands, the device using SiO2 and ZnO film obtained via sol-gel exhibits an additional band in the UV range centered at 350 nm which can be attributed to excitonic emission. These emission bands of ZnO can transfer their energy when a proper dopant is present. For the devices produced the voltage-current characteristics were measured in a specific range of applied voltage. (C) 2007 Elsevier B.V. All rights reserved.

Electroluminescence of a device based on europium beta-diketonate with phosphine oxide complex

Rare earth (RE) ions have spectroscopic characteristics to emit light in narrow lines, which makes RE complexes with organic ligands candidates for full color OLED (Organic Light Emitting Diode) applications. In particular, beta-diketone rare earth (RE(3+)) complexes show high fluorescence emission efficiency due to the high absorption coefficient of the beta-diketone and energy transfer to the central ion. In this work, the fabrication and the electroluminescent properties of devices containing a double and triple-layer OLED using a new beta-diketone complex, [Eu(bmdm)(3)(tppo)(2)], as transporting and emitting layers are compared and discussed. The double and triple-layer devices based on this complex present the following configurations respectively: device 1: ITO/TPD (40 nm)/[Eu(bmdm)(3)(tppo)(2)] (40 nm)/Al (150 nm); device 2: ITO/TPD (40 nm)/[Eu(bmdm)(3) (tppo)(2)] (40 nm)/Alq(3) (20 nm)/Al (150 nm) and device 3: ITO/TPD (40 nm)/bmdm-ligand (40 nm)/Al (150 nm), were TPD is (N,N'-diphenyl-N,N'-bis(3-methylphenyl)-1,1-biphenil-4,4-diamine) and bmdm is butyl methoxy-dibenzoyl-methane. All the films were deposited by thermal evaporation carried out in a high vacuum system. These devices exhibit high intensity photo- (PL) and electro-luminescent (EL) emission. Electroluminescence spectra show emission from Eu(3+) ions attributed to the (5)D(0) to (7)F(J) (J = 0, 1, 2, 3 and 4) transitions with the hypersensitive (5)D(o) -> (7)F(2) transition (around 612 nm) as the most prominent one. Moreover, a transition from (5)D(1) to (7)F(1) is also observed around 538 nm. The OLED light emission was almost linear with the current density. The EL CIE chromaticity coordinates (X = 0.66 and Y = 0.33) show the dominant wavelength, lambda(d) = 609 nm, and the color gamut achieved by this device is 0.99 in the CIE color space. (c) 2006 Elsevier B.V. All rights reserved.

Low voltage electroluminescence of terbium- and thulium-doped zinc oxide films

Strong interest in developing technology for visual information. stimulates research for thin film electroluminescent devices. Here, for the first time, we report that thulium- and terbium-doped zinc-oxide films are suitable for electroluminescence applications. Two different devices were assembled as lTO/LiF/ZnO:RE/LiF/Al or ITO/SiO2/ZnO:RE/SiO2/Al, where ZnO:RE is a film of zinc oxide containing 10 at% of Tb3+ or Tm3+. Electroluminescence spectra show that besides a broad emission band with maximum around 650 nm assigned to ZnO, also emission lines from Tb3+ at 484 nm (D-5(4) -> F-7(6)), 543 nm (D-5(4) -> F-7(6)), and 589 nm (D-5(4) -> F-7(4)), or from Tm3+ at 478 nm ((1)G(4) -> H-3(6)), and 511 mn (D-1(2) -> H-3(5)) were detected. Intensity of emission as function of applied voltage and current-voltage characteristic are shown and discussed. (c) 2005 Elsevier B.V. All rights reserved.

Effect of ion concentration of ionomer in electron injection layer of polymer light-emitting devices

Polymer light-emitting devices (PLEDs) with poly(2-methoxy-5-hexyloxy)-p-phenylenevinylene (OC1OC6-PPV) as the emissive layer were studied with an electron injection layer of ionomers consisting of copolymers of styrene and methylmethacrylate (PS/PMMA) with 3, 6 and 8 mol% degree of sulfonation. The ionomers were able to form very thin films over the emissive layer, with less than 30 nm. Additionally, the presence of ion pairs of ionomer suppresses the tendency toward dewetting of the thin film of ionomer (similar to 10 nm) which can cause malfunction of the device. The effect of the ionomers was investigated as a function of the ion content. The devices performance, characterized by their current density and luminance intensity versus voltage, showed a remarkable increase with the ionomer layer up to 6 mol% of ionic groups, decreasing after that for the 8 mol% ionomer device. The study of the impedance spectroscopy in the frequency range from 0.1 to 10(6) Hz showed that the injection phenomena dominate over the transport in the electroluminescent polymer bulk. (c) 2006 Elsevier B.V. All rights reserved.

Light emitting diodes containing Langmuir-Blodgett films of copolymer of a poly(p-phenylene-vinylene) derivative and poly(octaneoxide)

The properties of Langmuir and Langmuir-Blodgett (LB) films from a block copolymer with polyethylene oxide and phenylene-vinylene moieties are reported. The LB films were successfully transferred onto several types of substrates, with sufficient quality to allow for evaporation of a metallic electrode on top of the LB films to produce polymer light emitting diodes (PLEDs). The photoluminescence and electroluminescence spectra of the LB film and device were similar, featuring an emission at ca. 475 nm, from which we could infer that the emission mechanisms are essentially the same as in poly(p-phenylene) derivatives. Analogously to other PLEDs the current versus voltage characteristics of the LB-based device could be explained with the Arkhipov model according to which charge transport occurs among localized sites. The implications for nanotechnology of the level of control that may be achieved with LB devices will also be discussed.

Incorporation of a liquid crystal to enhance the luminescence properties of Langmuir-Blodgett films of OC1OC6-PPV

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Langmuir and langmuir-blodgett films of polyfluorenes and their use in polymer light-emitting diodes

The Langmuir and Langmuir-Blodgett (LB) film properties of two polyfluorene derivatives, namely poly(2,7-9,9'-dihexylfluorene-dyil) (PDHF) and poly(9,9 dihexylfluorene-dyil-vynilene-alt-1,4-phenylene-vyninele) (PDHF-PV), are reported. Surface pressure (Pi-A) and surface potential (Delta V-A) isotherms indicated that PDHF-PV forms true monolayers at the air/water interface, but PDHF does not. LB films could be transferred onto various types of substrate for both PDHF and PDHF-PV. Only the LB films from PDHF-PV could withstand deposition of a layer of evaporated metal to form a light-emitting diode (PLED), which had typical rectifying characteristics and emitted blue light. It is inferred that the ability of the polymer to form true monomolecular layers at the air/water interface seems to be associated with the viability of the LB films in PLEDs.

Fabrication of novel light-emitting devices based on green-phosphor/conductive-polymer composites

We report on light-emitting devices based on a green-phosphor compound (Mn-doped zinc silicate, Zn2SiO4: Mn) dispersed in a conductive polymeric blend (poly-o-methoxyaniline/polyvinylene fluoride, POMA/PVDF-TrFE). The devices exhibited high luminance in the green, good stability and homogeneous brilliance over effective areas up to 5 cm(2). The electroluminescence (EL) spectrum presented essentially the same characteristics as the photoluminescence (PL) and cathodoluminescence spectra, indicating that the light emission originates from decay of the same excited species, regardless of the excitation source. Operating characteristics were analyzed with current density - voltage (J - V) and luminance voltage ( L - V) curves to investigate the nature of the electroluminescence of the active material, which is still not completely understood.

Changeover during in situ compositional modulation of hexacyanoferrate (Prussian Blue) material

This paper describes the importance of (H2O)(6) clusters in controlling the properties of hexacyanoferrate (Prussian Blue) materials. A careful in situ study of compositional changes by using electrogravimetric techniques (in ac and dc modes) in hexacyanoferrates containing K+ alkali metals reveals the existence of a changeover in the properties of these films in a narrow potential range. Control of the compositional variation of the changeover is dependent on the K+ stoichiometric number in the compound structure. However, a specific K+ occupation in the compound structure activates the occupation of the (H2O)(6) cluster by H3O+ and/or H+, causing the changeover in the properties of hexacyanoferrate film. Thus, the information thus obtained is very useful for understanding the mechanisms involved in the electrochemical reversible switch between ferrimagnetism/paramagnetism, semiconductor/metal and electroluminescence/nonelectroluminescence properties of molecular cyanide materials.

Interface formation of nanostructured heterojunction SnO 2:Eu/GaAs and electronic transport properties

Thin films of tin dioxide (SnO2) are deposited by the sol-gel-dip-coating technique, along with GaAs layers, deposited by the resistive evaporation technique. The as-built heterojunction has potential application in optoelectronic devices, combining the emission from the rare-earth doped transparent oxide (Eu3+-doped SnO2 presents very efficient red emission) with a high mobility semiconductor. The advantage of this structure is the possibility of separation of the rare-earth emission centers from the electron scattering, leading to a strongly indicated combination for electroluminescence. Electrical characterization of the heterojunction SnO2:Eu/GaAs shows a significant conductivity increase when compared to the conductivity of the individual films, and the monochromatic light irradiation (266 nm) at low temperature of the heterojunction GaAs/SnO2:Eu leads to intense conductivity increase. Scanning electron microscopy (SEM) of the heterojunction cross section shows high adherence and good morphological quality of the interfaces substrate/SnO2 and SnO2/GaAs, even though the atomic force microscopy (AFM) image of the GaAs surface shows disordered particles, which increases with sample thickness. On the other hand, the good morphology of the SnO2:Eu surface, shown by AFM, assures the good electrical performance of the heterojunction. The observed improvement on the electrical transport properties is probably related to the formation of short conduction channels at the semiconductors interface, which may exhibit two-dimensional electron gas (2DEG) behavior. © 2012 Elsevier B.V. All rights reserved.

Complexos aniônicos contendo európio ou gandolínio e beta-dicetonas aplicados aos estudos foto e/ou eletroluminescentes de sólidos e filmes

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Photo-Induced Conductivity of Heterojunction GaAs/Rare-Earth Doped SnO2

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Desenvolvimento de um sistema para caracterização de dispositivos eletroluminescentes

The materials designed to be used in electroluminescent (EL) devices construction are studied and improved since 1936. Great interests in the development of this kind of devices are mainly due to its low power consumption, flexibility, low cost and easy processing. One class of ELs devices with these characteristics are produced by employing a organic-polymeric/inorganic composite from a conductive polymer blend and an inorganic electroluminescent material (Zn2SiO4:Mn) dispersed in the polymeric matrix. This kind of device operates in d.c. or a.c. potentials, with EL of hundreds candela in the green region of the visible spectrum. However, few studies on the light emission were performed for these devices. In order to characterize devices made from composites, in this work is proposed a method of characterizing the electroluminescence associated with the impedance spectroscopy technique. To implement the technique of impedance spectroscopy was employ an experimental setup consisting of a source of a.c. voltage, an oscilloscope, and a reference resistor. Associated with this system, was use a photo diode and an analog electrometer to characterize the emitted light signal from the sample. The system was implemented allows characterization by impedance spectroscopy in the frequency range from 0.2 Hz up to 2 MHz and voltage amplitudes of 5 mV up to 20 kV. This system permits, at the same time, measurement of the RMS value of the luminance for devices in frequency range from 20 Hz up to 2 MHz. To test the system efficiency, an EL device was characterized showing analogous results to those reported in literature. By doing this, was demonstrated the efficiency of the system for electroluminescence characterization associated with the electrical characterization by impedance spectroscopy, for devices