Photoluminescence study of new lanthanide complexes with benzeneseleninic acids

New lanthanide complexes with benzeneseleninic (ABSe) and 4-chloro-benzeneseleninic (ABSeCl) acids have been synthesized and characterized by elemental analysis, infrared and UV-visible spectroscopies. The emission spectra of the trivalent europium complexes presented the typical electronic (5)D(0) -> (7)F(j) transitions of the ion (J = 0-4). The ground-state geometries of the europium complexes have been calculated by using the Sparkle/AM1 model. From these results, the 4f-4f intensity parameters and energies of the ligand singlet and triplet excited states have been obtained. The lower emission quantum yield for the [Eu(ABSe)(3)(H(2)O)(2)](H(2)O)(2) compound, as compared to the [Eu(Al(3)SeCl)(3)(H(2)O)(2)] one, can be associated to the higher numbers of water molecules, in the first and second coordination spheres, that contribute to the luminescence quenching. The [Eu(Al(3)Se)(3)(H(2)O)(2)](H(2)O)(2) complex presents an intermediate state whose energy difference with respect to the first excited singlet state is resonant with three phonons from the water molecules, favouring a multiphonon relaxation process from the singlet state followed by a fast internal conversion process; this effect is less pronounced in the complex with the ABSeCl ligand. The luminescence decay curves of the gadolinium complexes indicate that the level responsible for the intramolecular energy transfer process has a triplet character for both compounds. The nephelauxetic effect in these compounds was investigated under the light of a recently proposed covalency scale based on the concept of overlap polarizability of the chemical bond. (C) 2009 Elsevier B.V. All rights reserved.

Modulation of trans-to-cis photoisomerization and photoluminescence of 1,2-bis(4-pyridyl)ethylene or 4-styrylpyridine coordinated to fac-tricarbonyl(5-chloro-1,10-phenathroline)rhenium(I)

Photochemical and photophysical properties of fac-[Re(CO)(3)(Clphen)(trans-L)](+) complexes, Clphen = 5-chloro-1,10-phenathroline and L = 1,2-bis(4-pyridyl)ethylene, bpe, or 4-styrylpyridine, stpy, were investigated to complement the understanding of intramolecular energy transfer process in tricarbonyl rhenium(I) complexes having an electron withdrawing group attached to polypyridyl ligands. These new compounds were synthesized, characterized and the photoisomerization quantum yields were accurately determined by (1)H NMR spectroscopy. The true quantum yields for fac-[Re(CO)(3)(Clphen) (trans-bpe)](+) were constant (Phi = 0.55) at all investigated irradiation wavelengths. However, for fac-[Re(CO)(3)(Clphen)(trans-stpy)](+), similar true quantum yields were observed only at higher energy irradiation (Phi(313 nm) = 0.53 and Phi(365 nm) = 0.57), but it decreased significantly at 404 nm (Phi = 0.41). These results indicated different deactivation pathways for the trans-stpy complex photoisomerization. Quantum yields decreased as the (3)IL(trans-L) and (3)MLCT(Re -> NN) excited states become closer and the behavior was discussed in terms of the excited state energy gaps. Additionally, luminescence properties of photoproducts, fac-[Re(CO)(3)(Clphen)(cis-L)](+), were also investigated in different environments to analyze the relative energy of the (3)MLCT(Re -> Clphen) excited state for each compound. (C) 2011 Elsevier B.V. All rights reserved.

Photophysical properties and quantum chemical studies of poly(2,7-9,9'-dihexylfluorene-dyil)

This work reports the photophysical properties (excitation and fluorescence spectra, fluorescence quantum yield, fluorescence lifetimes) of the poly(2,7-9,9'-dihexylfluorene-dyil) in dilute solutions of four solvents (toluene, tetrahydrofuran, chloroform and ethyl acetate) as well as the properties in solid state. Photoluminescence showed spectra characteristic of disordered α-backbone chain conformation. Simulation of the electronic absorption spectra of oligomers containing 1 to 11 mers showed that the critical conjugation length is between 6 and 7 mers. We also estimated the theoretical dipole moments which indicated that a coil conformation is formed with 8 repeating units per turn. We also showed that some energy transfer process appears in solid state which decreases the emission lifetime. Furthermore, based on luminescent response of the systems herein studied and electroluminescent behavior reported on literature, both photo and electroluminescence emissions arise from the same emissive units.

Influence of metallic nanoparticles on electric-dipole and magnetic-dipole transitions of Eu(3+) doped germanate glasses

Luminescence properties of Eu(3+) doped germanate glasses containing either silver or gold nanoparticles (NPs) were investigated for excitation at 405 nm. Enhanced emissions and luminescence quenching of the Eu(3+) transitions in the range from 570 to 720 nm were observed for samples having various concentrations of metallic NPs. Electric-dipole and magnetic-dipole transitions that originate from the Eu(3+) level (5)D(0) exhibit large enhancement due to the presence of the metallic NPs. The results suggest that the magnetic response of rare-earth doped metal-dielectric composites at optical frequencies can be as strong as their electric response due to the confinement of the optical magnetic field. (C) 2010 American Institute of Physics. [doi:10.1063/1.3431347]

Frequency upconversion luminescence from Yb(+3)-Tm(+3) codoped PbO-GeO(2) glasses containing silver nanoparticles

Infrared-to-visible and infrared-to-infrared frequency upconversion processes in Yb(3+)-Tm(3+) doped PbO-GeO(2) glasses containing silver nanoparticles (NPs) were investigated. The experiments were performed by exciting the samples with a diode laser operating at 980 nm (in resonance with the Yb(3+) transition (2)F(7/2)->(2)F(5/2)) and observing the photoluminescence (PL) in the visible and infrared regions due to energy transfer from Yb(3+) to Tm(3+) ions followed by excited state absorption in the Tm3+ ions. The intensified local field in the vicinity of the metallic NPs contributes for enhancement in the PL intensity at 480 nm (Tm(3+) :(1)G(4)->(3)H(6)) and at 800 nm (Tm(3+) : (3)H(4) -> (3)H(6)). (C) 2009 American Institute of Physics. [doi:10.1063/1.3211300]

Enhanced luminescence of Tb(3+)/Eu(3+) doped tellurium oxide glass containing silver nanostructures

We report on energy transfer studies in terbium (Tb(3+))-europium (Eu(3+)) doped TeO(2)-ZnO-Na(2)O-PbO glass containing silver nanostructures. The samples excitation was made using ultraviolet radiation at 355 nm. Luminescence spectra were recorded from approximate to 480 to approximate to 700 nm. Enhanced Eu(3+) luminescence at approximate to 590 nm (transition (5)D(0)-(7)F(1)) and approximate to 614 nm (transition (5)D(0)-(7)F(2)) are observed. The large luminescence enhancement was obtained due to the simultaneous contribution of the Tb(3+)-Eu(3+) energy transfer and the contribution of the intensified local field on the Eu(3+) ions located near silver nanostructures.

Study of the influence of indium segregation on the optical properties of InGaAs/GaAs quantum wells via split-operator method

In the case of quantum wells, the indium segregation leads to complex potential profiles that are hardly considered in the majority of the theoretical models. The authors demonstrated that the split-operator method is useful tool for obtaining the electronic properties in these cases. Particularly, they studied the influence of the indium surface segregation in optical properties of InGaAs/GaAs quantum wells. Photoluminescence measurements were carried out for a set of InGaAs/GaAs quantum wells and compared to the results obtained theoretically via split-operator method, showing a good agreement.

Zero-phonon emission and magnetic polaron parameters in EuTe

A phonon structure in the photoluminescence of EuTe was discovered, with a well-defined zero-phonon emission line (ZPL). The ZPL redshifts linearly with the intensity of applied magnetic field, indicating spin relaxation of the photoexcited electron, and saturates at a lower magnetic field than the optical absorption bandgap, which is attributed to formation of magnetic polarons. From the difference in these saturation fields, the zero-field polaron binding energy and radius are estimated to be 43 meV and 3.2 (in units of the EuTe lattice parameter), respectively. (C) 2011 American Institute of Physics. [doi:10.1063/1.3634030]

Defect-induced effects on carrier migration through one-dimensional poly(para-phenylenevinylene) chains

Defects in one-dimensional (1D) systems can be intrinsically distinct from its three-dimensional counterparts, and polymer films are good candidates for showing both extremes that are difficult to individuate in the experimental data. We study theoretically the impact of simple hydrogen and oxygen defects on the electron transport properties of one-dimensional poly(para-phenylenevinylene) chains through a multiscale technique, starting from classical structural simulations for crystalline films to extensive ab initio calculations within density functional theory for the defects in single crystalline-constrained chains. The most disruptive effect on carrier transport comes from conjugation breaking imposed by the overcoordination of a carbon atom in the vinyl group independently from the chemical nature of the defect. The particular case of the [C=O] (keto-defect) shows in addition unexpected electron-hole separation, suggesting that the experimentally detected photoluminescence bleaching and photoconductivity enhancement could be due to exciton dissociation caused by the 1D characteristics of the defect.

Anisotropic Confinement, Electronic Coupling and Strain Induced Effects Detected by Valence-Band Anisotropy in Self-Assembled Quantum Dots

A method to determine the effects of the geometry and lateral ordering on the electronic properties of an array of one-dimensional self-assembled quantum dots is discussed. A model that takes into account the valence-band anisotropic effective masses and strain effects must be used to describe the behavior of the photoluminescence emission, proposed as a clean tool for the characterization of dot anisotropy and/or inter-dot coupling. Under special growth conditions, such as substrate temperature and Arsenic background, 1D chains of In(0.4)Ga(0.6) As quantum dots were grown by molecular beam epitaxy. Grazing-incidence X-ray diffraction measurements directly evidence the strong strain anisotropy due to the formation of quantum dot chains, probed by polarization-resolved low-temperature photoluminescence. The results are in fair good agreement with the proposed model.

Nonlinear spectra of ZnO: reverse saturable, two- and three-photon absorption

We present a broadband (460-980 nm) analysis of the nonlinear absorption processes in bulk ZnO, a large-bandgap material with potential blue-to-UV photonic device applications. Using an optical parametric amplifier we generated tunable 1-kHz repetition rate laser pulses and employed the Z-scan technique to investigate the nonlinear absorption spectrum of ZnO. For excitation wavelengths below 500 nm, we observed reverse saturable absorption due to one-photon excitation of the sample, agreeing with rate-equation modeling. Two-and three-photon absorption were observed from 540 to 980 nm. We also determined the spectral regions exhibiting mixture of nonlinear absorption mechanisms, which were confirmed by photoluminescence measurements. (C) 2010 Optical Society of America

A study of disorder effects in random (Al(x)Ga(1-x)As)(n)(Al(y)Ga(1-y)As)(m) superlattices embedded in a wide parabolic potential

A photoluminescence (PL) study of the individual electron states localized in a random potential is performed in artificially disordered superlattices embedded in a wide parabolic well. The valence band bowing of the parabolic potential provides a variation of the emission energies which splits the optical transitions corresponding to different wells within the random potential. The blueshift of the PL lines emitted by individual random wells, observed with increasing disorder strength, is demonstrated. The variation of temperature and magnetic field allowed for the behavior of the electrons localized in individual wells of the random potential to be distinguished.

Structural and optical analysis of GaAsP/GaP core-shell nanowires

The structural and optical properties of GaAsP/GaP core-shell nanowires grown by gas source molecular beam epitaxy were investigated by transmission electron microscopy, Raman spectroscopy, photoluminescence (PL), and magneto-PL. The effects of surface depletion and compositional variations in the ternary alloy manifested as a redshift in GaAsP PL upon surface passivation, and a decrease in redshift in PL in the presence of a magnetic field due to spatial confinement of carriers.

Substrate/semiconductor interface effects on the emission efficiency of luminescent polymers

The importance of interface effects for organic devices has long been recognized, but getting detailed knowledge of the extent of such effects remains a major challenge because of the difficulty in distinguishing from bulk effects. This paper addresses the interface effects on the emission efficiency of poly(p-phenylene vinylene) (PPV), by producing layer-by-layer (LBL) films of PPV alternated with dodecylbenzenesulfonate. Films with thickness varying from similar to 15 to 225 nm had the structural defects controlled empirically by converting the films at two temperatures, 110 and 230 degrees C, while the optical properties were characterized by using optical absorption, photoluminescence (PL), and photoluminescence excitation spectra. Blueshifts in the absorption and PL spectra for LBL films with less than 25 bilayers (<40-50 nm) pointed to a larger number of PPV segments with low conjugation degree, regardless of the conversion temperature. For these thin films, the mean free-path for diffusion of photoexcited carriers decreased, and energy transfer may have been hampered owing to the low mobility of the excited carriers. The emission efficiency was then found to depend on the concentration of structural defects, i.e., on the conversion temperature. For thick films with more than 25 bilayers, on the other hand, the PL signal did not depend on the PPV conversion temperature. We also checked that the interface effects were not caused by waveguiding properties of the excited light. Overall, the electronic states at the interface were more localized, and this applied to film thickness of up to 40-50 nm. Because this is a typical film thickness in devices, the implication from the findings here is that interface phenomena should be a primary concern for the design of any organic device. (C) 2011 American Institute of Physics. [doi:10.1063/1.3622143]

Spectroscopic evidence of extended states in the quantized Hall phase of weakly coupled GaAs/AlGaAs multilayers

The influence of interlayer coupling on the formation of the quantized Hall phase at the filling factor nu=2 was studied in multilayer GaAs/AlGaAs heterostructures. The disorder broadened Gaussian photoluminescence line due to localized electrons was found in the quantized Hall phase of the isolated multi-quanturn-well structure. On the other hand, the quantized Hall phase of weakly coupled multilayers emitted an unexpected asymmetrical line similar to that observed in metallic electron systems. We demonstrated that the observed asymmetry is caused by the partial population of extended electron states formed in the insulating quantized Hall phase due to spin-assisted interlayer percolation. A sharp decrease in the single-particle scattering time associated with these extended states was observed for the filling factor nu=2. (C) 2008 American Institute of Physics. [DOI: 10.1063/1.2978194]