Exceptionally efficient organic light emitting devices using high refractive index substrates.

Organic light emitting devices (OLEDs) are now used in commercial cell phones and flat screen displays, but may become even more successful in lighting applications, in which large area, high efficiency, long lifetime and low cost are essential. Due to the relatively high refractive index of the organic layers, conventional planar bottom emitting OLEDs have a low outcoupling efficiency. Various approaches for enhancing the optical outcoupling efficiency of bottom emitting OLEDs have been introduced in the literature. In this paper we demonstrate a green bottom emitting OLED with a record external quantum efficiency (42%) and luminous efficacy (183 lm/W). This OLED is based on a high index substrate and a thick electron transport layer (ETL) which uses electrical doping. The efficient light outcoupling is modeled by optical simulations.

The complex excited-state behavior of a polyspirobifluorene derivative: the role of spiroconjugation and mixed charge transfer character on excited-state stabilization and radiative lifetime.

In this study, we report on the unusual fluorescence decay of an alkoxy-substituted polyspirobifluorene. Excited state behavior has been probed as a function of time, using femtosecond photobleaching, single photon counting, and streak camera techniques. Unusually complex decay kinetics are observed, which strongly depend on solvent viscosity and polarity, featuring decay components in both the tens of picoseconds and in the nanosecond time domain. These findings are explained by the consequences of spiroconjugation in combination with excited-state conformational relaxation. We propose that exciton wave function delocalization into the spiro units effectively traps the exciton, allowing it to relax further into a highly emissive state with a very long lifetime as compared to non-spiroconjugated polymer analogues. Frontier molecular orbitals and exciton orbitals have been calculated using a first principles density functional theory (DFT) approach. These results confirm the importance of spiroconjugation as both the highest occupied molecular orbital (HOMO) and the (lowest) exciton level are not localized on the polymer backbone but strongly extend into the side fluorene groups of the spirobifluorene units. The results of our calculations are very sensitive to the substitution pattern on the spirobifluorene units, in particular when oxygen is included. This finding may lead to new materials of this kind with optimized charge carrier transport properties and high luminescence quantum yields.

Cationic bis-cyclometallated iridium(III) phenanthroline complexes with pendant fluorenyl substituents: synthesis, redox, photophysical properties and light-emitting cells.

We report the synthesis, characterisation, photophysical and electrochemical properties of a series of cationic cyclometallated Ir(III) complexes of general formula [Ir(ppy)(2)(phen)]PF(6) (ppy=2-phenylpyridine, phen=a substituted phenanthroline). A feature of these complexes is that the phen ligands are substituted with one or two 9,9-dihexylfluorenyl substituents to provide extended pi conjugation, for example, the 3-[2-(9,9-dihexylfluorenyl)]phenanthroline and 3,8-bis[2-(9,9-dihexylfluorenyl)]phenanthroline ligands afford complexes 6 and 9, respectively. A single-crystal X-ray diffraction study of a related complex 18 containing the 3,8-bis(4-iodophenyl)phenanthroline ligand, revealed an octahedral coordination of the Ir atom, in which the metallated C atoms of the ppy ligands occupy cis positions. The complexes 6 and 9 displayed reversible oxidation waves in cyclic voltammetric studies (E(ox)(1/2)=+1.18 and +1.20 V, respectively, versus Ag/Ag(+) in CH(2)Cl(2)) assigned to the metal-centred Ir(III)/Ir(IV) couple. The complexes exhibit strong absorption in the UV region in solution spectra, due to spin-allowed ligand-centred (LC) (1)pi-pi* transitions; moderately intense bands occur at approximately 360-390 nm which are red-shifted with increased ligand length. The photoluminescence spectra of all the complexes were characterised by a broad band at lambda(max) approximately 595 nm assigned to a combination of (3)MLCT and (3)pi-->pi* states. The long emission lifetimes (in the microsecond time-scale) are indicative of phosphorescence: the increased ligand conjugation length in complexes 9 and 17 leads to increased lifetimes for the complexes (tau=2.56 and 2.57 micros in MeCN, respectively) compared to monofluorenyl analogues 6 and 15 (tau=1.43 and 1.39 micros, respectively). DFT calculations of the geometries and electronic structures of complexes 6', 9' (for both singlet ground state (S(0)) and triplet first excited (T(1)) states) and 18 have been performed. In the singlet ground state (S(0)) HOMO orbitals in the complexes are spread between the Ir atom and benzene rings of the phenylpyridine ligand, whereas the LUMO is mainly located on the phenanthroline ligand. Analysis of orbital localisations for the first excited (T(1)) state have been performed and compared with spectroscopic data. Spin-coated light-emitting cells (LECs) have been fabricated with the device structures ITO/PEDOT:PSS/Ir complex/Al, or Ba capped with Al (ITO=indium tin oxide, PEDOT=poly(3,4-ethylenedioxythiophene), PSS=poly(styrene) sulfonate). A maximum brightness efficiency of 9 cd A(-1) has been attained at a bias of 9 V for 17 with a Ba/Al cathode. The devices operated in air with no reduction in efficiency after storage for one week in air.

Long-range resonantly enhanced triplet formation in luminescent polymers doped with iridium complexes.

The current drive to produce cheap, flexible plastic displays has led to rapid improvements in device efficiency. Inclusion of highly phosphorescent heavy-metal organic complexes as dopants ensures that both singlet and triplet excitations formed on charge recombination can be used efficiently to emit light. However, the inclusion of these dopants affects the photophysics of the host in a surprising way, generating a ten- to twenty- fold instantaneous increase in the number of host triplet states, independent of host triplet energy, quenching up to 95% of all singlet states. Once created however, these triplets are only weakly quenched by the same mechanism. We ascribe this to a resonant, remote intermolecular heavy-atom effect that greatly increases the inter-system crossing rate of the host polymer arising through the strong overlap of the delocalized pi orbitals of the host and ligands. This mechanism competes effectively with Förster energy transfer, and operates over large distances.

Regarding the origin of the delayed fluorescence of conjugated polymers.

In the first part of this work we revisit and reevaluate the experimental data that lead to the assignment of the origin of the delayed fluorescence (DF) to triplet-triplet annihilation for polyfluorene and to geminate pair recombination in the case of the ladder-type polyparaphenylene (MeLPPP); the ambiguity of this classification is unveiled. Next, new data about the DF of MeLPPP under applied electric field are presented. Here, the DF intensity completely recovers once the field is turned off, which rules out geminate pairs as the origin of the DF and in turn provides clear evidence of the triplet-triplet annihilation picture. Finally, we show and discuss how recombination of space charge layers may also give rise to electric field induced delayed fluorescence, whereby the formation of these space charge layers strongly depends on device configuration and purity of the materials.

Triplet build in and decay of isolated polyspirobifluorene chains in dilute solution.

The triplet kinetics of a conjugated polymer, polyspirobifluorene, have been studied using time resolved photoinduced absorption spectroscopy and gated emission delayed fluorescence. Working on isolated polymer chains in dilute solution, we pay particular attention to the buildup and decay of the triplet states following intersystem crossing from the excited singlet state. Confirmation of intersystem crossing as a monomolecular cold process has been made. At high excitation powers an initial fast decay of the triplet has been observed; this is attributed to intrachain triplet-triplet annihilation. From this observation we estimate the lower bound of the intersystem crossing yield as 1.2%. We also calculate the intrachain annihilation constant to be (2.9+/-0.1)x 10(8) cm(3) s(-1).

Carbazole compounds as host materials for triplet emitters in organic light-emitting diodes: polymer hosts for high-efficiency light-emitting diodes.

A carbazole homopolymer and carbazole copolymers based on 9,9'-dialkyl-[3,3']-bicarbazolyl, 2,5-diphenyl-[1,3,4]-oxadiazole and 9,9-bis(4-[3,7-dimethyloctyloxy]phenyl)fluorene were synthesized and their electrical and photophysical properties were characterized with respect to their application as host in phosphorescent polymer light-emitting diodes. It is shown that the triplet energy of a polymer depends on the specific connections between its building blocks. Without changing the composition of the polymer, its triplet energy can be increased from 2.3 to 2.6 eV by changing the way in which the different building blocks are coupled together. For poly(9-vinylcarbazole) (PVK), a carbazole polymer often used as host for high-energy triplet emitters in polymer light-emitting diodes, a large hole-injection barrier of about 1 eV exists due to the low-lying HOMO level of PVK. For all carbazole polymers presented here, the HOMO levels are much closer to the Fermi level of a commonly used anode such as ITO and/or a commonly used hole-injection layer such as PEDOT:PSS. This makes high current densities and consequently high luminance levels possible at moderate applied voltages in polymer light-emitting diodes. A double-layer polymer light-emitting diode is constructed comprising a PEDOT:PSS layer as hole-injection layer and a carbazole-oxadiazole copolymer doped with a green triplet emitter as emissive layer that shows an efficacy of 23 cd/A independent of current density and light output.