275 research outputs found
Publisher's Note: "Solution processed multilayer polymer light-emitting diodes based on different molecular weight host" (vol 109, 074516, 2011)
Solution processed multilayer polymer light-emitting diodes (PLEDs) based on different molecular weight host have been investigated. A PLED based on high molecular weight poly (vinyl carbazole) PVKH and low molecular weight poly (vinyl carbazole) PVKL, doped with iridium, tris(2-phenylpyidine) Ir(ppy)3 as a host-guest emitting layer (EML), shows a dramatic increase in device efficiency. When the PVKH was used as a hole transport electron blocking layer (HT-EBL), effective electron blocking was achieved, which leads to an increase exciton population in the phosphorescent zone. The use of low molecular weight PVKL as a host material in the top layer prevents barrier formation for hole transport from the poly(3,4-ethylenedioxy-thiophene) (PEDOT)–EBL to the EML. External quantum efficiency of 11%, current efficiencies of 38 cd/A, power efficiency of 13 lm/W and brightness of 7000 cd/m2, were obtained. The effect of the PVKH layer on the electrical and optical device characteristics was investigated. Simulation of the optical outcoupling using SETFOS 3.1 software is in agreed with the observed results and allowed us to predict the emissive dipole location and distribution in the EML layer. The effect of the PVKH on the exciton quenching by the electrodes was also investigated using time resolved fluorescence photon counting, which indicates weak exciton quenching by the PEDOT layer and the device enhancement predominantly achieved by exciton confinement in the emissive layer
Multifrequency EPR study of charge transport in doped polyaniline
Polyaniline highly doped with acrylamido-2-methyl-1-propanesulphonic (PANI-AMPSA) and camphorsulfonic (PANI-CSA) acids have been studied at X- (9.50 GHz) and K- (37.5 GHz) bands EPR. Localized Curie-like and mobile Pauli-like spin charge carriers are stabilized in amorphous and crystalline regions of the samples. AC conductivity contributed from these paramagnetic centers was determined. It was shown that, in contrast with PANI-AMPSA, PANI-CSA with higher both d.c. and a.c. conductivity is a more ordered metal with more rigid and planar polymer chains
On the triplet state of poly(N-vinylcarbazole)
Triplet state properties including transient triplet absorption spectrum, intersystem crossing yields in solution at room temperature and phosphorescence spectra, quantum yields and lifetimes at low temperature as well as singlet oxygen yields were obtained for poly(N-vinylcarbazole) (PVK) in 2-methyl-tetrahydrofuran (2-MeTHF), cyclohexane or benzene. The results allow the determination of the energy value for the lowest lying triplet state and also show that triplet formation and deactivation is a minor route for relaxation of the lowest excited singlet state of PVK. In addition, they show the triplet state is at higher energy than reported heavy metal dopants used for electrophosphorescent devices, such that if this is used as a host it will not quench their luminescence.http://www.sciencedirect.com/science/article/B6TFN-4DTTJJC-7/1/b605edb9859b607f1a9b1c1348af029
The electronic structure of polyaniline and doped phases studied by soft X-ray absorption and emission spectroscopies
The electronic structure of the conjugated polymer, polyaniline, has been
studied by resonant and nonresonant X-ray emission spectroscopy using
synchrotron radiation for the excitation. The measurements were made on
polyaniline and a few doped (protonated) phases for both the carbon and
nitrogen contents. The resonant X-ray emission spectra show depletion of the
{\pi} electron bands due to the selective excitation which enhances the effect
of symmetry selection rules. The valence band structures in the X-ray emission
spectra attributed to the {\pi} bands show unambiguous changes of the
electronic structure upon protonation. By comparing to X-ray absorption
measurements, the chemical bonding and electronic configuration is
characterized.Comment: 8 pages, 8 pictures,
http://jcp.aip.org/resource/1/jcpsa6/v111/i10/p4756_s
Intramolecular Hydrogen Bonding in Thermally Activated Delayed Fluorescence Emitters: Is There Evidence Beyond Reasonable Doubt?
Intramolecular hydrogen bonding between donor and acceptor segments in thermally activated delayed fluorescence (TADF) materials is now frequently employed to─purportedly─rigidify the structure and improve the emission performance of these materials. However, direct evidence for these intramolecular interactions is often lacking or ambiguous, leading to assertions that are largely speculative. Here we investigate a series of TADF-active materials incorporating pyridine, which bestows the potential ability to form intramolecular H-bonding interactions. Despite possible indications of H-bonding from an X-ray analysis, an array of other experimental investigations proved largely inconclusive. Instead, after examining computational potential energy surfaces of the donor–acceptor torsion angle we conclude that the pyridine group primarily alleviates steric congestion in our case, rather than enabling an H-bond interaction as elsewhere assumed. We suggest that many previously reported “H-bonding” TADF materials featuring similar chemical motifs may instead operate similarly and that investigation of potential energy surfaces should become a key feature of future studies
Conformational Dependence of Triplet Energies in Rotationally Hindered N‐ and S‐Heterocyclic Dimers: New Design and Measurement Rules for High Triplet Energy OLED Host Materials
A series of four heterocyclic dimers has been synthesized, with twisted geometries imposed across the central linking bond by ortho‐alkoxy chains. These include two isomeric bicarbazoles, a bis(dibenzothiophene‐S,S‐dioxide) and a bis(thioxanthene‐S,S‐dioxide). Spectroscopic and electrochemical methods, supported by density functional theory, have given detailed insights into how para‐ vs. meta‐ vs. broken conjugation, and electron‐rich vs. electron‐poor heterocycles impact the HOMO–LUMO gap and singlet and triplet energies. Crucially for applications as OLED hosts, the triplet energy (ET) of these molecules was found to vary significantly between dilute polymer films and neat films, related to conformational demands of the molecules in the solid state. One of the bicarbazole species shows a variation in ET of 0.24 eV in the different media—sufficiently large to “make‐or‐break” an OLED device—with similar discrepancies found between neat films and frozen solution measurements of other previously reported OLED hosts. From consolidated optical and optoelectronic investigations of different host/dopant combinations, we identify that only the lower ET values measured in neat films give a reliable indicator of host/guest compatibility. This work also provides new molecular design rules for obtaining very high ET materials and controlling their HOMO and LUMO energies
Electron correlation effects in electron-hole recombination in organic light-emitting diodes
We develop a general theory of electron--hole recombination in organic light
emitting diodes that leads to formation of emissive singlet excitons and
nonemissive triplet excitons. We briefly review other existing theories and
show how our approach is substantively different from these theories. Using an
exact time-dependent approach to the interchain/intermolecular charge-transfer
within a long-range interacting model we find that, (i) the relative yield of
the singlet exciton in polymers is considerably larger than the 25% predicted
from statistical considerations, (ii) the singlet exciton yield increases with
chain length in oligomers, and, (iii) in small molecules containing nitrogen
heteroatoms, the relative yield of the singlet exciton is considerably smaller
and may be even close to 25%. The above results are independent of whether or
not the bond-charge repulsion, X_perp, is included in the interchain part of
the Hamiltonian for the two-chain system. The larger (smaller) yield of the
singlet (triplet) exciton in carbon-based long-chain polymers is a consequence
of both its ionic (covalent) nature and smaller (larger) binding energy. In
nitrogen containing monomers, wavefunctions are closer to the noninteracting
limit, and this decreases (increases) the relative yield of the singlet
(triplet) exciton. Our results are in qualitative agreement with
electroluminescence experiments involving both molecular and polymeric light
emitters. The time-dependent approach developed here for describing
intermolecular charge-transfer processes is completely general and may be
applied to many other such processes.Comment: 19 pages, 11 figure
Conformationally-restricted bicarbazoles with phenylene bridges displaying deep-blue emission and high triplet energies: systematic structure-property relationships
The synthesis is reported of twelve new symmetrical carbazole dimers in which the carbazole units are linked via 1,4-phenylene spacers. There are two distinct series of compounds based on the position on the carbazole ring where the phenylene spacer is attached: this is either at carbazole C(3) (series 1a-1f) or at C(2) (series 2a-2f). The central phenylene ring is substituted with either two methyl, two methoxy or two cyano substituents which impart an intramolecular torsional angle between the phenylene and carbazole rings, thereby limiting the extent of π-conjugation between the carbazole units, and raising the triplet energies of the molecules to ET 2.6-3.0 eV, as determined from their phosphorescence spectra at 80 K. Structure-property relationships were studied by UV-vis and fluorescence spectroscopy, cyclic voltammetry and theoretical calculations. A notable observation is that substitution at the 2-position of carbazole (linear conjugation) exerts control over the position of the HOMO, while substitution at the 3-position of carbazole (meta conjugation) allows greater control over the LUMO. X-ray crystal structures are reported for two of the bicarbazoles. Compound 2d is shown to be a suitable host for the sky-blue emitter FIrpic in PhOLEDs, with improved device performance compared to CBP as host
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