Exciton confinement in organic dendrimer quantum wells for opto-electronic applications

Journal ArticleOrganic dendrimers are a fascinating new class of materials for opto-electronic applications. We present coupled electronic oscillator calculations on novel nanoscale conjugated dendrimers for use in organic light-emitting diodes. Strong confinement of excitations at the center of the dendrimers is observed, which accounts for the dependence of intermolecular interactions and charge transport on the degree of branching of the dendrimer. The calculated absorption spectra are in excellent agreement with the measured data and show that benzene rings are shared between excitations on the linear segments of the hyperbranched molecules. The coupled electronic oscillator approach is ideally suited to treat large dendritic molecules

Control of mobility in molecular organic semiconductors by dendrimer generation

Journal ArticleConjugated dendrimers are of interest as novel materials for light-emitting diodes. They consist of a luminescent chromophore at the core with highly branched conjugated dendron sidegroups. In these materials, light emission occurs from the core and is independent of generation. The dendron branching controls the separation between the chromophores. We present here a family of conjugated dendrimers and investigate the effect of dendron branching on light emission and charge transport. We apply a number of transport measurement techniques to thin films of a conjugated dendrimer in a light-emitting diode configuration to determine the effect of chromophore spacing on charge transport. We find that the mobility is reduced by two orders of magnitude as the size of the molecule doubles with increased branching or dendrimer generation. The degree of branching allows a unique control of mobility by molecular structure. An increase in chromophore separation also results in a reduction of intermolecular interactions, which reduces the red emission tail in film photoluminescence. We find that the steady-state charge transport is well described by a simple device model incorporating the effect of generation, and use the materials to shed light on the interpretation of transient electroluminescence data. We demonstrate the significance of the ability to tune the mobility in bilayer devices, where a more balanced charge transport can be achieved

Effect of interchain coupling on conducting polymer luminescence: excimers in derivatives of poly(phenylene vinylene)

Optical excitation of a chain in a polymer film may result in formation of an excimer, a superposition of on-chain excitons and charge-transfer excitons on the originally excited chain and a neighboring chain. The excimer emission is red-shifted compared to that of an on-chain exciton by an amount depending on the interchain coupling $t_\perp$. Setting up the excimer wavefunction and calculating the red shift, we determine average $t_\perp$ values, referred to a monomer, of 0.52 eV and 0.16 eV for poly(2,5-hexyloxy $p$-phenylene cyanovinylene), CN-PPV, and poly[2-methoxy, 5-(2'-ethyl-hexyloxy)-1, 4 p-phenylene vinylene], MEH-PPV, respectively, and use them to determine the effect of interchain distance on the emission.Comment: 10 pages, RevTeX, 1 PS figure, replaced version of cond-mat/9707095, accepted for publication in Phys. Rev. B, Rapid Communicatio

Photonic band structure and emission characteristics of a metal-backed polymeric distributed feedback laser

Copyright © 2002 American Institute of Physics. This article may be downloaded for personal use only. Any other use requires prior permission of the author and the American Institute of Physics. The following article appeared in Applied Physics Letters 81 (2002) and may be found at http://link.aip.org/link/?APPLAB/81/954/1Optical losses associated with the metallic contacts necessary for charge injection are an obstacle to the development of an electrically pumped polymer laser. We show that it may be possible to overcome these losses by demonstrating the operation of a distributed-feedback polymer laser fabricated upon a silver substrate. The device lasing threshold was ~150 times greater than that of an otherwise similar metal-free device, though similar to early polymer lasers. The device emission characteristics correlated well with the measured photonic band structure, allowing an explanation of the effect of the microstructure on device operation

Operating characteristics of a semiconducting polymer laser pumped by a microchip laser

Copyright © 2003 American Institute of Physics. This article may be downloaded for personal use only. Any other use requires prior permission of the author and the American Institute of Physics. The following article appeared in Applied Physics Letters 82 (2003) and may be found at http://link.aip.org/link/?APPLAB/82/313/1We report the demonstration of a compact, all-solid-state polymer laser system featuring a microchip laser as the pump source. The laser was configured as a surface-emitting, two-dimensional distributed feedback laser, based on the conjugated polymer poly(2-methoxy-5-(2'-ethylhexyloxy)-1,4-phenylene vinylene). Pulsed, band-edge lasing was observed at 636 nm above a threshold pump energy of 4 nJ. The laser exhibited an energy slope efficiency of 6.8%, with a maximum output energy of 1.12 nJ at a pump energy of 20.4 nJ. The output beam had an azimuthally polarized annular profile with a beam quality factor (M2) of 2.2, close to the theoretical value of the lowest-order Laguerre–Gaussian and Bessel–Gaussian annular modes. We explain the origin of the azimuthal polarization as due to a coherent combination of the resonant fields supported by the two gratings

Effect of generation on the electronic properties of light-emitting dendrimers

We have compared the optical and electronic properties of a series of porphyrin centred dendrimers containing stilbene dendrons. The first and second generation dendrimers could be spin-coated from solution to form good quality thin films. Incorporation into single layer light-emitting diodes gave red-light emission with maximum external quantum efficiencies of 0.02% and 0.04% for the first and second generation dendrimers respectively. We have determined by photoluminescence studies that energy can be transferred efficiently from the stilbene dendrons to the porphyrin core and that PL emission is from the core. Cyclic voltammetry studies on the dendrimers show that the reductions are porphyrin centred with the dendrons only affecting the rate of heterogeneous electron transfer between the electrode and the dendrimers. This suggests that charge mobility within a dendrimer film in an LED will be affected by the porphyrin edge to porphyrin edge distance. We have studied the hydrodynamic radii of the dendrimers by gel permeation chromatography and found as expected that the average porphyrin edge to dendron edge distance increases with generation This is consistent with the slowing of heterogeneous electron transfer observed in the cyclic voltammetry on increasing the generation number and suggests that the dendrons are interleaved in the solid state to facilitate charge transport

Oral Region Homologies in Paleozoic Crinoids and Other Plesiomorphic Pentaradial Echinoderms

The phylogenetic relationships between major groups of plesiomorphic pentaradial echinoderms, the Paleozoic crinoids, blastozoans, and edrioasteroids, are poorly understood because of a lack of widely recognized homologies. Here, we present newly recognized oral region homologies, based on the Universal Elemental Homology model for skeletal plates, in a wide range of fossil taxa. The oral region of echinoderms is mainly composed of the axial, or ambulacral, skeleton, which apparently evolved more slowly than the extraxial skeleton that forms the majority of the body. Recent phylogenetic hypotheses have focused on characters of the extraxial skeleton, which may have evolved too rapidly to preserve obvious homologies across all these groups. The axial skeleton conserved homologous suites of characters shared between various edrioasteroids and specific blastozoans, and between other blastozoans and crinoids. Although individual plates can be inferred as homologous, no directly overlapping suites of characters are shared between edrioasteroids and crinoids. Six different systems of mouth (peristome) plate organization (Peristomial Border Systems) are defined. These include four different systems based on the arrangement of the interradially-positioned oral plates and their peristomial cover plates, where PBS A1 occurs only in plesiomorphic edrioasteroids, PBS A2 occurs in plesiomorphic edrioasteroids and blastozoans, and PBS A3 and PBS A4 occur in blastozoans and crinoids. The other two systems have radially-positioned uniserial oral frame plates in construction of the mouth frame. PBS B1 has both orals and uniserial oral frame plates and occurs in edrioasterid and possibly edrioblastoid edrioasteroids, whereas PBS B2 has exclusively uniserial oral frame plates and is found in isorophid edrioasteroids and imbricate and gogiid blastozoans. These different types of mouth frame construction offer potential synapomorphies to aid in parsimony-based phylogenetics for exploring branching order among stem groups on the echinoderm tree of life

Surface plasmon-polariton mediated emission from phosphorescent dendrimer light-emitting diodes

Copyright © 2006 American Institute of Physics. This article may be downloaded for personal use only. Any other use requires prior permission of the author and the American Institute of Physics. The following article appeared in Applied Physics Letters 88 (2006) and may be found at http://link.aip.org/link/?APPLAB/88/161105/1We present experimental results showing electroluminescence from a dendrimer based organic light-emitting diode (OLED) mediated via surface plasmon polariton (SPP) modes. A combination of angle dependent electroluminescence, photoluminescence, and reflectance measurements is used to identify emission originating from the guided modes of the device. It is found that the SPP modes, which are usually nonradiative, are coupled to light by a wavelength scale periodic microstructure. It is demonstrated that the necessary microstructure can be readily fabricated by solvent-assisted micromoulding. Our results indicate that such an approach may offer a means to increase the efficiency of dendrimer based OLEDs

Low threshold edge emitting polymer distributed feedback laser based on a square lattice

Copyright © 2005 American Institute of Physics. This article may be downloaded for personal use only. Any other use requires prior permission of the author and the American Institute of Physics. The following article appeared in Applied Physics Letters 86 (2005) and may be found at http://link.aip.org/link/?APPLAB/86/161102/1We report the demonstration of a low-threshold, edge-emitting polymer distributed feedback laser based on a square lattice. The lattice constant was 268 nm, which corresponds to a lattice line spacing in the ΓM symmetry direction of the Brillouin zone of 189 nm. The latter was employed to provide feedback at 630 nm via a first order diffraction process. The device operated on two longitudinal modes, which were situated on the band-edge near the M symmetry point. The two modes had thresholds of 0.66 nJ and 1.2 nJ—significantly lower than comparable surface-emitting DFB lasers. Angle dependent photoluminescence experiments were performed to investigate the effect of the square lattice on the laser operation and the origin of the low threshold

Blue, surface-emitting, distributed feedback polyfluorene lasers

Copyright © 2003 American Institute of Physics. This article may be downloaded for personal use only. Any other use requires prior permission of the author and the American Institute of Physics. The following article appeared in Applied Physics Letters 83 (2003) and may be found at http://link.aip.org/link/?APPLAB/83/2118/1We report the fabrication of optically-pumped solid-state distributed feedback lasers utilizing two blue-light-emitting semiconducting polyfluorenes as gain media. The lasers were readily fabricated by solution deposition of thin polymer films on top of gratings etched into fused silica substrates. A compact Nd:YVO4 microchip laser was used as the pump source for the two polymers studied, and lasing was achieved at 455 and 465 nm. Low threshold energies, ≥ 4 nJ per pulse, were obtained. The emission characteristics of the lasers are described along with the results of additional experiments that investigate in more detail the effect of the grating microstructure on polymer light emission