Mechanism of point-defect diffusion in a two-dimensional colloidal crystal

The dynamics and mechanism of migration of a vacancy point defect in a two-dimensional (2D) colloidal crystal are studied using numerical simulations. We find that the migration of a vacancy is always realized by topology switching between its different configurations. From the temperature dependence of the topology switch frequencies, we obtain the activation energies for possible topology transitions associated with the vacancy diffusion in the 2D crystal. (C) 2011 American Institute of Physics. [doi:10.1063/1.3615287]

Structural and optical properties of rare earth-doped (Ba(0.77)Ca(0.23))(1-x)(Sm, Nd, Pr, Yb)(x)TiO(3)

The structural, dielectric, and vibrational properties of pure and rare earth (RE)-doped Ba(0.77) Ca(0.23)TiO(3) (BCT23; RE = Nd, Sm, Pr, Yb) ceramics obtained via solid-state reaction were investigated. The pure and RE-doped BCT23 ceramics sintered at 1450 degrees C in air for 4 h showed a dense microstructure in all ceramics. The use of RE ions as dopants introduced lattice-parameter changes that manifested in the reduction of the volume of the unit cell. RE-doped BCT23 samples exhibit a more homogenous microstructure due to the absence of a Ti-rich phase in the grain boundaries as demonstrated by scanning electron microscopy imaging. The incorporation of REs led to perturbations of the local symmetry of TiO(6) octahedra and the creation of a new Raman mode. The results of Raman scattering measurements indicated that the Curie temperature of the ferroelectric phase transition depends on the RE ion and ion content, with the Curie temperature shifting toward lower values as the RE content increases, with the exception of Yb(3+) doping, which did not affect the ferroelectric phase transition temperature. The phase transition behavior is explained using the standard soft mode model. Electronic paramagnetic resonance measurements showed the existence of Ti vacancies in the structure of RE-doped BCT23. Defects are created via charge compensation mechanisms due to the incorporation of elements with a different valence state relative to the ions of the pure BCT23 host. It is concluded that the Ti vacancies are responsible for the activation of the Raman mode at 840 cm(-1), which is in agreement with lattice dynamics calculations. (c) 2011 American Institute of Physics. [doi:10.1063/1.3594710]

Two-photon absorption spectra of carotenoids compounds

Carotenoids are biosynthetic organic pigments that constitute an important class of one-dimensional pi-conjugated organic molecules with enormous potential for application in biophotonic devices. In this context, we studied the degenerate two-photon absorption (2PA) cross-section spectra of two carotenoid compounds (beta-carotene and beta-apo-8'-carotenal) employing the conventional and white-light-continuum Z-scan techniques and quantum chemistry calculations. Because carotenoids coexist at room temperature as a mixture of isomers, the 2PA spectra reported here are due to samples containing a distribution of isomers, presenting distinct conjugation length and conformation. We show that these compounds present a defined structure on the 2PA spectra, that peaks at 650 nm with an absorption cross-section of approximately 5000 GM, for both compounds. In addition, we observed a 2PA band at 990 nm for beta-apo-8'-carotenal, which was attributed to a overlapping of I(I)B(u) +-like and 2(I)Ag(-)-like states, which are strongly one- and two-photon allowed, respectively. Spectroscopic parameters of the electronic transitions to singlet-excited states, which are directly related to photophysical properties of these compounds, were obtained by fitting the 2PA spectra using the sum-over-states approach. The analysis and interpretations of the 2PA spectra of the investigated carotenoids were supported by theoretical predictions of one- and two-photon transitions carried out using the response functions formalism within the density functional theory framework, using the long-range corrected CAM-B3LYP functional. (C) 2011 American Institute of Physics. [doi:10.1063/1.3590157]

Experimental and theoretical study of two-photon absorption in nitrofuran derivatives: Promising compounds for photochemotherapy

We report experimental and theoretical studies of the two-photon absorption spectrum of two nitrofuran derivatives: nitrofurantoine, (1-(5-nitro-2-furfurilideneamine)-hidantoine) and quinifuryl, 2-(5`-nitro-2`-furanyl) ethenyl-4-{N-[4`-(N,N-diethylamino)-1`-methylbutyl]carbamoyl} quinoline. Both molecules are representative of a family of 5-nitrofuran-ethenyl-quinoline drugs that have been demonstrated to display high toxicity to various species of transformed cells in the dark. We determine the two-photon absorption cross-section for both compounds, from 560 to 880 nm, which present peak values of 64 GM for quinifuryl and 20 GM for nitrofurantoine (1 GM = 1 x 10(-50) cm(4).s.photon(-1)). Besides, theoretical calculations employing the linear and quadratic response functions were carried out at the density functional theory level to aid the interpretations of the experimental results. The theoretical results yielded oscillator strengths, two-photon transition probabilities, and transition energies, which are in good agreement with the experimental data. A higher number of allowed electronic transitions was identified for quinifuryl in comparison to nitrofurantoine by the theoretical calculations. Due to the planar structure of both compounds, the differences in the two-photon absorption cross-section values are a consequence of their distinct conjugation lengths. (c) 2011 American Institute of Physics. [doi:10.1063/1.3514911]

Universal resistance capacitance crossover in current-voltage characteristics for unshunted array of overdamped Nb-AlOx-Nb Josephson junctions

We report on some unusual behavior of the measured current-voltage characteristics (CVC) in artificially prepared two-dimensional unshunted array of overdamped Nb-AlO(x)-Nb Josephson junctions. The obtained nonlinear CVC are found to exhibit a pronounced (and practically temperature independent) crossover at some current I(cr) = (1/2 beta(C)-1)I(C) from a resistance R dominated state with V(R)=R root I(2)-I(C)(2) below I(cr) to a capacitance C dominated state with V(C) = root(h) over bar /4eC root I-I(C) above I(cr). The origin of the observed behavior is discussed within a single-plaquette approximation assuming the conventional resistively shunted junction model with a finite capacitance and the Ambegaokar-Baratoff relation for the critical current of the single junction. (C) 2010 American Institute of Physics. [doi: 10.1063/1.3407566]

Three-dimensional fabrication of optically active microstructures containing an electroluminescent polymer

Microfabrication via two-photon absorption polymerization is a technique to design complex microstructures in a simple and fast way. The applications of such structures range from mechanics to photonics to biology, depending on the dopant material and its specific properties. In this paper, we use two-photon absorption polymerization to fabricate optically active microstructures containing the conductive and luminescent polymer poly(2-methoxy-5-(2'-ethylhexyloxy)-1,4-phenylenevinylene) (MEH-PPV). We verify that MEH-PPV retains its optical activity and is distributed throughout the microstructure after fabrication. The microstructures retain the emission characteristics of MEH-PPV and allow waveguiding of locally excited fluorescence when fabricated on top of low refractive index substrates. (C) 2009 American Institute of Physics. [doi: 10.1063/1.3232207]

The role of oxygen vacancy in the photoluminescence property at room temperature of the CaTiO(3)

In this paper, electron paramagnetic resonance, photoluminescence (PL) emission, and quantum mechanical calculations were used to observe and understand the structural order-disorder of CaTiO(3), paying special attention to the role of oxygen vacancy. The PL phenomenon at room temperature of CaTiO(3) is directly influenced by the presence of oxygen vacancies that yield structural order-disorder. These oxygen vacancies bonded at Ti and/or Ca induce new electronic states inside the band gap. Ordered and disordered CaTiO(3) was obtained by the polymeric precursor method. (C) 2009 American Institute of Physics. [DOI: 10.1063/1.3190524]

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]

Microwave dielectric permittivity and photoluminescence of Eu(2)O(3) doped laser heated pedestal growth Ta(2)O(5) fibers

We report the microwave dielectric properties and photoluminescence of undoped and europium oxide doped Ta(2)O(5) fibers, grown by laser heated pedestal growth technique. The effects of Eu(2)O(3) doping (1-3 mol %) on the structural, optical, and dielectric properties were investigated. At a frequency of 5 GHz, the undoped material exhibits a dielectric permittivity of 21 and for Eu(2)O(3) doped Ta(2)O(5) samples it increases, reaching up to 36 for the highest doping concentration. Nevertheless, the dielectric losses maintain a very low value. For this wide band gap oxide, Eu(3+) optical activation was achieved and the emission is observed up to room temperature. Thus, the transparency and high permittivity make this material promising for electronic devices and microwave applications. (c) 2008 American Institute of Physics.

Substrate orientation effect on potential fluctuations in multiquantum wells of GaAs/AlGaAs

The photoluminescence (PL) technique as a function of temperature and excitation intensity was used to study the optical properties of multiquantum wells (MQWs) of GaAs/Al(x)Ga(1-x)As grown by molecular beam epitaxy on GaAs substrates oriented in the [100], [311]A, and [311]B directions. The asymmetry presented by the PL spectra of the MQWs with an apparent exponential tail in the lower-energy side and the unusual behavior of the PL peak energy versus temperature (blueshift) at low temperatures are explained by the exciton localization in the confinement potential fluctuations of the heterostructures. The PL peak energy dependence with temperature was fitted by the expression proposed by Passler [Phys. Status Solidi B 200, 155 (1997)] by subtracting the term sigma(2)(E)/k(B)T, which considers the presence of potential fluctuations. It can be verified from the PL line shape, the full width at half maximum of PL spectra, the sigma(E) values obtained from the adjustment of experimental points, and the blueshift maximum values that the samples grown in the [311]A/B directions have higher potential fluctuation amplitude than the sample grown in the [100] direction. This indicates a higher degree of the superficial corrugations for the MQWs grown in the [311] direction. (C) 2008 American Institute of Physics.

Fluoride-modified electrical properties of lead borate glasses and electrochemically induced crystallization in the glassy state

Lead fluoroborate glasses were prepared by the melt-quenching technique and characterized in terms of (micro)structural and electrical properties. The study was conducted on as prepared as well as temperature- and/or electric field-treated glass samples. The results show that, in the as-prepared glassy-state materials, electrical conductivity improved with increasing the PbF(2) glass content. This result involves both an increase of the fluoride charge carrier density and, especially, a decrease of the activation energy from a glass structure expansion improving charge carrier mobility. Moreover, for the electric field-treated glass samples, surface crystallization was observed even below the glass transition temperature. As previously proposed in literature, and shown here, the occurrence of this phenomenon arose from an electrochemically induced redox reaction at the electrodes, followed by crystallite nucleation. Once nucleated, growth of beta-PbF(2) crystallites, with the indication of incorporating reduced lead ions (Pb(+)), was both (micro)structurally and electrically detectable and analyzed. The overall crystallization-associated features observed here adapt well with the floppy-rigid model that has been proposed to further complete the original continuous-random-network model by Zachariasen for closely addressing not only glasses' structure but also crystallization mechanism. Finally, the crystallization-modified kinetic picture of the glasses' electrical properties, through application of polarization/depolarization measurements originally combined with impedance spectroscopy, was extensively explored. (c) 2008 American Institute of Physics.

Effect of Mn concentration and atomic structure on the magnetic properties of Ge thin films

This work reports on the magnetic properties of Ge(100-x)Mn(x) (x=0-24 at. %) films prepared by cosputtering a Ge+Mn target and submitted to cumulative thermal annealing treatments up to 500 degrees C. Both as-deposited and annealed films were investigated by means of compositional analysis, Raman scattering spectroscopy, magnetic force microscopy, superconducting quantum interference device magnetometry, and electrical resistivity measurements. All as-deposited films (either pure or containing Mn) exhibit an amorphous structure, which changes to crystalline as the annealing treatments are performed at increasing temperatures. In fact, the magnetic properties of the present Ge(100-x)Mn(x) films are very sensitive to the Mn content and whether their atomic structure is amorphous or crystalline. More specifically: whereas the amorphous Ge(100-x)Mn(x) films (with high x) present a characteristic spin glass behavior at low temperature; after crystallization, the films (with moderate Mn contents) are ferromagnetic at room temperature. Moreover, the magnetic behavior of the films scales with their Mn concentration and tends to be more pronounced after crystallization. Finally, the semiconducting behavior of the films, experienced by previous optical studies, was confirmed through electrical measurements, which also indicate the dependence of the resistivity with the atomic composition of the films. (C) 2010 American Institute of Physics. [doi: 10.1063/1.3520661]

The role of quantum confinement and crystalline structure on excitonic lifetimes in silicon nanoclusters

The emission energy dependence of the photoluminescence (PL) decay rate at room temperature has been studied in Si nanoclusters (Si-ncl) embedded in Si oxide matrices obtained by thermal annealing of substoichiometric Si oxide layers Si(y)O(1-y), y=(0.36,0.39,0.42), at various annealing temperatures (T(a)) and gas atmospheres. Raman scattering measurements give evidence for the formation of amorphous Si-ncl at T(a)=900 degrees C and of crystalline Si-ncl for T(a)=1000 degrees C and 1100 degrees C. For T(a)=1100 degrees C, the energy dispersion of the PL decay rate does not depend on sample fabrication conditions and follows previously reported behavior. For lower T(a), the rate becomes dependent on fabrication conditions and less energy dispersive. The effects are attributed to exciton localization and decoherence leading to the suppression of quantum confinement and the enhancement of nonradiative recombination in disordered and amorphous Si-ncl. (C) 2010 American Institute of Physics. [doi: 10.1063/1.3457900]

Quantum yield excitation spectrum (UV-visible) of CdSe/ZnS core-shell quantum dots by thermal lens spectrometry

A recently developed thermal lens spectrometry configuration has been used to study CdSe/ZnS core-shell quantum dots (QDs) suspended in toluene and tetrahydrofuran (THF) solvents. The special features of this configuration make it very attractive to measure fluorescence quantum yield (eta) excitation spectrum since it simplifies the measurement procedure and consequently improve the accuracy. Furthermore, the precision reached is much higher than in conventional photoluminescence (PL) technique. Two methods, called reference sample and multiwavelength have been applied to determine eta, varying excitation wavelength in the UV-visible region (between 335-543 nm). The eta and PL spectra are practically independent of the excitation wavelength. For CdSe/ZnS QDs suspended in toluene we have obtained eta=76 +/- 2%. In addition, the aging effect on eta and PL has been studied over a 200 h period for QDs suspended in THF. (C) 2010 American Institute of Physics. [doi:10.1063/1.3343517]