Electron injection in "electron-only" devices based on a symmetric metal/silole/metal structure

We report on electron injection from two different metal electrodes into three silole derivatives, namely 2,5-di-(3-biphenyl)-1,1-dimethyl-3,4-diphenylsilacyclopentadiene (PPSPP), 1,2-bis(1-methyl-2,3,4,5,-tetraphenylsilacyclopentadienyl) ethane (2PSP) and 2,5-bis-(2', 2'-bipyridin-6-yl)-1, 1-dimethyl-3,4-diphenylsilacyclopentadiene (PyPySPyPy), previously employed as emissive and electron transport materials in molecular organic light-emitting diodes (MOLEDs). Silole films were sandwiched between symmetric Mg:Ag or bilayer CsF-Al electrodes. The steady-state current density-voltage characteristics were measured as a function of the silole layer thickness for the two cathodes. The trap-free space-charge-limited current based on time-of-flight measurements compared with the injected electron current for PyPySPyPy indicated that Mg:Ag contacts limit the injected current, while CsF-Al contacts behave as quasi-ohmic contacts. Similar findings were obtained for 2PSP and PPSPP allowing steady-state derived electron mobility parameters to be extracted. Based on space-charge-limited conduction analysis of the measured current-voltage characteristics, PyPySPyPy is found to be a superior electron transporting silole with approximately an order of magnitude higher electron mobility (2.0/spl times/10/sup -4/ cm/sup 2//Vs) compared with those of 2PSP (2.4/spl times/10/sup -5/ cm/sup 2//Vs) and PPSPP (5.2/spl times/10/sup -5/ cm/sup 2//Vs), which is significantly higher than that of the prototype electron transport material tris (8-hydroxyquinolinolato) aluminum (III) (Alq/sub 3/) (6.5/spl times/10/sup -7/ cm/sup 2//Vs) at 0.6 MV/cm.     

High performance organic light emitting diodes using substoichiometric tungsten oxide as efficient hole injection layer

In this work we demonstrate the unique hole injection and transport properties of a substoichiometric tungsten oxide with precise stoichiometry, in particular WO_2.5, obtained after the controlled hydrogen reduction during growth of tungsten oxide, using a simple hot-wire vapor deposition technique. We present clear evidence that tungsten suboxide exhibits metallic character and that an almost zero hole injection barrier exists at the anode/polymer interface due to the formation/occupation of electronic gap states near the Fermi level after oxide’s reduction. These states greatly facilitate hole injection and charge generation/electron extraction enabling the demonstration of extremely efficient hole only devices. WO_2.5 films exhibit metallic-like conductivity and, thus, can also enhance charge transport at both anode and cathode interfaces. Electroluminescent devices using WO_2.5 as both, hole and electron injection layer, and poly[(9,9-dioctylfluorenyl-2,7-diyl)-co-(1,4-benzo-{2,1′,3}-thiadiazole)] (F8BT) as the emissive layer exhibited high efficiencies up to 7 cd/A and 4.5 lm/W, while, stability studies revealed that these devices were extremely stable, since they were operating without encapsulation in air for more than 700 h.     

Atomic layer deposited zirconium oxide electron injection layer for efficient organic light emitting diodes

In this work, we demonstrate efficient polyfluorene-based light emitting diodes on which conformal, thin ZrO₂ layers, formed by atomic layer deposition at a relatively low temperature (175 °C), in order to avoid introducing any damage in the organic under layer, efficiently inject electrons from their high lying conduction band to the polymer’s LUMO. An optimal thickness of 2 nm for ZrO₂ results in a threefold improvement in luminous current efficiency compared to the reference device. The relationship between the thickness of the ZrO₂ layer and the device operational characteristics is further investigated and the possible reasons for the improved device performance are discussed based on the experimental results obtained by a combination of photoemission spectroscopy and electrical/optical measurements.     

Large work function shift of organic semiconductors inducing enhanced interfacial electron transfer in organic optoelectronics enabled by porphyrin aggregated nanostructures

We report on large work function shifts induced by the coverage of several organic semiconducting （OSC） films commonly used in organic light emitting diodes （OLEDs） and organic photovoltaics （OPVs） with a porphyrin aggregated layer. The insertion between the organic film and the aluminum cathode of an aggregated layer based on the meso-tetrakis（1-methylpyridinium-4-yl） porphyrin chloride （porphyrin 1）, with its molecules adopting a face-to-face orientation parallel to the organic substrate, results in a significant shift of the OSC work function towards lower values due to the formation of a large interfacial dipole and induces large enhancement of either the OLED or OPV device efficiency. OLEDs based on poly[（9,9-dioctylfluorenyl-2,7-diyl）-co-（1,4-benzo-2,1＇,3-thiadiazole）J （F8BT） and incorporating the porphyrin 1 at the cathode interface exhibited current efficiency values up to 13.8 cd/A, an almost three-fold improvement over the efficiency of 4.5 cd/A of the reference device. Accordingly, OPVs based on poly（3- hexylthiophene） （P3HT）, [6,6]-phenyl-C61 butyric acid methyl ester （PC61BM） and porphyrin 1 increased their external quantum efficiencies to 4.4% relative to 2.7% for the reference device without the porphyrin layer. The incorporation of a layer based on the zinc meso-tetrakis （1-methylpyridinium-4-yl）porphyrin chloride （porphyrin 2）, with its molecules adopting an edge-to-edge orientation, also introduced improvements, albeit more modest in all cases, highlighting the impact of molecular orientation.     

Reduction of Tungsten Oxide: A Path Towards Dual Functionality Utilization for Efficient Anode and Cathode Interfacial Layers in Organic Light‐Emitting Diodes

Here, we report on the dual functionality of tungsten oxide for application as an efficient electron and hole injection/transport layer in organic light‐emitting diodes (OLEDs). We demonstrate hybrid polymer light‐emitting diodes (Hy‐PLEDs), based on a polyfluorene copolymer, by inserting a very thin layer of a partially reduced tungsten oxide, WO_2.5, at the polymer/Al cathode interface to serve as an electron injection and transport layer. Significantly improved current densities, luminances, and luminous efficiencies were achieved, primarily as a result of improved electron injection at the interface with Al and transport to the lowest unoccupied molecular orbital (LUMO) of the polymer, with a corresponding lowering of the device driving voltage. Using a combination of optical absorption, ultraviolet spectoscopy, X‐ray photoelectron spectroscopy, and photovoltaic open circuit voltage measurements, we demonstrate that partial reduction of the WO₃ to WO_2.5 results in the appearance of new gap states just below the conduction band edge in the previously forbidden gap. The new gap states are proposed to act as a reservoir of donor electrons for enhanced injection and transport to the polymer LUMO and decrease the effective cathode workfunction. Moreover, when a thin tungsten oxide film in its fully oxidized state (WO₃) is inserted at the ITO anode/polymer interface, further improvement in device characteristics was achieved. Since both fully oxidized and partially reduced tungsten oxide layers can be deposited in the same chamber with well controlled morphology, this work paves the way for the facile fabrication of efficient and stable Hy‐OLEDs with excellent reproducibility.