Exciton Molecules in Quantum Wells: Influence of the Well Width Fluctuations

The influence of the well width fluctuations on the dependence of the binding energy of excitonic complexes in quantum wells is studied by using the path-integral Monte-Carlo technique. The results are compared with available experimental data and a good agreement is found.Postdoctoral researcher of FWO-Vlaanderen     

Synthesis and characterization of a polyfluorene containing carbazole and oxadiazole dipolar pendent groups and its application to electroluminescent devices

We have synthesized a blue‐light‐emitting polyfluorene (PF) derivative ( PF‐CBZ‐OXD ) that presents bulky hole‐transporting carbazole and electron‐transporting oxadiazole pendent groups functionalized at the C‐9 positions of alternating fluorene units. The results from photoluminescence and electrochemical measurements indicate that both the side chains and the PF main chain retain their own electronic characteristics in the copolymer. An electroluminescent device incorporating this polymer as the emitting layer was turned on at 4.5 V; it exhibited a stable blue emission with a maximum external quantum efficiency of 1.1%. Moreover, we doped PF‐CBZ‐OXD and its analogue PF‐TPA‐OXD with a red‐light‐emitting iridium phosphor for use as components of phosphorescent red‐light emitters to investigate the effect of the host's HOMO energy level on the degree of charge trapping and on the electrophosphorescent efficiency. We found that spectral overlap and individual energy level matching between the host and guest were both crucial features affecting the performance of the electroluminescence devices. Atomic force microscopy measurements indicated that the dipolar nature of PF‐CBZ‐OXD , in contrast to the general nonpolarity of polydialkylfluorenes, provided a stabilizing environment that allowed homogeneous dispersion of the polar iridium triplet dopant. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 2925–2937, 2007     

The “corset effect” of spin-lattice relaxation in polymer melts confined in nanoporous media

Linear polyethylene oxides with molecular weightsM _w of 1665 and 10170 confined in pores with variable diameters in a solid methacrylate matrix were studied by proton field-cycling nuclear magnetic resonance relaxometry. The pore diameter was varied in the range of 9–57 nm. In all cases, the spin-lattice relaxation time shows a frequency dependence close toT ₁∞ v^3/4 in the range ofv=3·10^?1-2·10¹ MHz as predicted by the tube-reptation model. This protonT ₁ dispersion essentially reproduces that found in a previous deuteron study (R. Kimmich, R.-O. Seitter, U. Beginn, M. Möller, N. Fatkullin: Chem. Phys. Lett. 307, 147, 1999). As a feature particularly characteristic for reptation, this finding suggests that reptation is the dominating chain dynamics mechanism under pore confinement in the corresponding time range. The absolute values of the spin-lattice relaxation times indicate that the diameter of the effective tubes in which reptation occurs is much smaller than the pore diameters on the time scale of spin-lattice relaxation experimens. An estimation leads to a valued ^*～0.5 nm. The impenetrability of the solid pore walls, the uncrossability of polymer chains (“excluded volume”) and the low value of the compressibility in polymer melts create the “corset effect” which reduces the lateral motions of polymer chains to a microscopic scale of only a few tenths of a nanometer.     

Anionic iron(II) alkoxides as initiators for the controlled ring‐opening polymerization of lactide

Hetero‐bimetallic Fe(II) alkoxide/aryloxides were evaluated as initiators for the ring‐opening polymerization of rac‐lactide. [(THF)NaFe(O^tBu)₃]₂ ( 1 ) and [(THF)₄Na₂Fe(2,6‐diisopropylphenolate)₄] ( 2 ) (THF = tetrahydrofuran) both polymerized lactide efficiently at room temperature, with complex 1 affording better control over the molecular weight parameters of the resultant polymer. At conversions below 70%, a linear increase in molecular weight with conversion was observed, indicative of a well‐controlled polymerization process. Complex 2 is the first example of a dianionic Fe(II) alkoxide and has been structurally characterized to reveal a distorted square planar FeO₄ array in which both Na counterions bridge two aryloxide ligands and are further complexed by two THF ligands. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3798–3803, 2003     

Förster energy transfer from poly(arylene–ethynylene)s to an erbium–porphyrin complex

We study the infrared emission at 1.54 μm of an organolanthanide complex, Er(III)-tetraphenylporphyrin [Er(TPP)acac], both as a result of direct optical excitation and via energy transfer from host π-conjugate polymers of type poly(arylene–ethynylene) [PAE]. In the first case, the emission of the neat complex is characterized in inert transparent materials and a value of the quantum yield at 1.54 μm φ_IR=4×10⁻⁴ is measured. Then, fluorescence resonance transfer is investigated in blends of Er(TPP)acac with PAEs by monitoring the quenching of the polymer fluorescence along with the enhancement of both the visible emission of the ligand and the near-infrared band of Er³⁺. These different procedures allow a detailed analysis of the transfer efficiency within a specific implementation of the Förster model for polymeric donors. The experimental values of the critical radius R₀, ranging from 1.3 to 2.5 nm for the different blends, are in good agreement with theory for a wide interval of the physical and spectroscopic parameters. This suggests that other mechanisms for excitation transfer do not play a significant role in these materials.     

cos πρ theorems for δ-subharmonic functions

For ϕ a δ-subharmonic function, sharp results are obtained that connectA(r, ϕ), B(r, ϕ) andT(r, ϕ), whereA(r, ϕ)=inf_|z|=r ϕ(z),B(r, ϕ)=sup_|z|=r ϕ(z), andT(r, ϕ) is the Nevanlinna characteristics.     

A geometrical constraint for capillary jet breakup

The formation of thinning filaments is commonly observed previously to the break-up of a very viscous jet. This paper shows that a fluid under capillary forces cannot break-up through the uniform collapse of a filament.     

Rapid and efficient synthesis of optically active pyrazoles under solvent-free conditions

2-Formyl glycals undergo rapid condensation with arylhydrazines under solvent-free conditions to give the corresponding optically pure 4-substituted pyrazoles in good yields with high selectivity. The stereochemistry of the products was assigned by various NMR experiments.     

Charge transport properties in carbon black/polymer composites

The charge transport properties of polymer matrix–carbon black composites are investigated in this study. Direct current conductivity is examined with varying parameters: the temperature and the conductive filler content. Conductivity data are analyzed by means of percolation theory, and both percolation threshold and critical exponent are determined at each of the examined temperatures. The temperature dependence of conductivity and the agreement of experimental results with the variable range hopping model reveal hopping conduction as the predominant transport mechanism, below and in the vicinity of the critical concentration of carbon black particles. At higher concentrations, the contribution of hopping transport to the overall conductivity is reduced and a balance between hopping and conduction via geometrical contact occurs. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2535–2545, 2007     

Polarization dynamics of intracavity frequency-doubled Nd:YAG laser

Experimental study of low-frequency dynamics of an intracavity frequency-doubled Nd:YAG laser demonstrates the influence of the interaction of orthogonally polarized modes, participating in frequency doubling (type II phase matching), on the stability of the laser output. At a sufficiently low pump rate and low conversion efficiency, the laser shows stable operation with a low noise level at the frequencies of relaxation oscillations. At a high pump power and/or a high conversion efficiency, the laser emission becomes unstable as a result of Hopf bifurcation at the frequencies of relaxation oscillations that are responsible for the anti-phase polarization dynamics of the laser.