NIR luminescent Er3+/Yb3+ co-doped SiO2-ZrO2 nanostructured planar and channel waveguides: Optical and structural properties

Optical and structural properties of planar and channel waveguides based on sol gel Er3+ and Yb3+ co-doped SiO2-ZrO2 are reported. Microstructured channels with high homogeneous surface profile were written onto the surface of multilayered densified films deposited on SiO2/Si substrates by a femtosecond laser etching technique. The densification of the planar waveguides was evaluated from changes in the refractive index and thickness, with full densification being achieved at 900 degrees C after annealing from 23 up to 500 min, depending on the ZrO2 content Crystal nucleation and growth took place together with densification, thereby producing transparent glass ceramic planar waveguides containing rare earth-doped ZrO2 nanocrystals dispersed in a silica-based glassy host Low roughness and crack-free surface as well as high confinement coefficient were achieved for all the compositions. Enhanced NIR luminescence of the Er3+ ions was observed for the Yb3+- codoped planar waveguides, denoting an efficient energy transfer from the Yb3+ to the Er3+ ion. (C) 2012 Elsevier B.V. All rights reserved.

Correlation of the Physicochemical and Structural Properties of pDNA/Cationic Liposome Complexes with Their in Vitro Transfection

In this study, we characterized the conventional physicochemical properties of the complexes formed by plasmid DNA (pDNA) and cationic liposomes (CL) composed of egg phosphatidylcholine (EPC), 1,2-dioleoyl-sn-glycero-3-phosphoethanolamine (DOPE), and 1,2-dioleoyl-3-trimethylammonium-propane (DOTAP) (50/25/25% molar ratio). We found that these properties are nearly unaffected at the studied ranges when the molar charge ratio (R-+/-) between the positive charge from the CL and negative charge from pDNA is not close to the isoneutrality region (R-+/- = 1). However, the results from in vitro transfection of HeLa cells showed important differences when R-+/- is varied, indicating that the relationships between the physicochemical and biological characteristics were not completely elucidated. To obtain information regarding possible liposome structural modifications, small-angle X-ray scattering (SAXS) experiments were performed as a function of R-+/- to obtain correlations between structural, physicochemical, and transfection properties. The SAXS results revealed that pDNA/CL complexes can be described as being composed of single bilayers, double bilayers, and multiple bilayers, depending on the R-+/- value. Interestingly, for R-+/- = 9, 6, and 3, the system is composed of single and double bilayers, and the fraction of the latter increases with the amount of DNA (or a decreasing R-+/-) in the system. This information is used to explain the transfection differences observed at an R-+/- = 9 as compared to R-+/- = 3 and 6. Close to the isoneutrality region (R-+/- = 1.8), there was an excess of pDNA, which induced the formation of a fraction of aggregates with multiple bilayers. These aggregates likely provide additional resistance against the release of pDNA during the transfection phenomenon, reflected as a decrease in the transfection level. The obtained results permitted proper correlation of the physicochemical and structural properties of pDNA/CL complexes with the in vitro transfection of HeLa cells by these complexes, contributing to a better understanding of the gene delivery process.

Electronic and magnetic properties of SnO2/CrO2 thin superlattices

In this article, using first-principles electronic structure calculations within the spin density functional theory, alternated magnetic and non-magnetic layers of rutile-CrO2 and rutile-SnO2 respectively, in a (CrO2) n (SnO2) n superlattice (SL) configuration, with n being the number of monolayers which are considered equal to 1, 2, ..., 10 are studied. A half-metallic behavior is observed for the (CrO2) n (SnO2) n SLs for all values of n. The ground state is found to be FM with a magnetic moment of 2 μB per chromium atom, and this result does not depend on the number of monolayers n. As the FM rutile-CrO2 is unstable at ambient temperature, and known to be stabilized when on top of SnO2, the authors suggest that (CrO2) n (SnO2) n SLs may be applied to spintronic technologies since they provide efficient spin-polarized carriers.

Controlling electronic and magnetic properties of ultra narrow multilayered nanowires

Interest in the study of magnetic/non-magnetic multilayered structures took a giant leap since Grünberg and his group established that the interlayer exchange coupling (IEC) is a function of the non-magnetic spacer width. This interest was further fuelled by the discovery of the phenomenal Giant Magnetoresistance (GMR) effect. In fact, in 2007 Albert Fert and Peter Grünberg were awarded the Nobel Prize in Physics for their contribution to the discovery of GMR. GMR is the key property that is being used in the read-head of the present day computer hard drive as it requires a high sensitivity in the detection of magnetic field. The recent increase in demand for device miniaturization encouraged researchers to look for GMR in nanoscale multilayered structures. In this context, one dimensional(1-D) multilayerd nanowire structure has shown tremendous promise as a viable candidate for ultra sensitive read head sensors. In fact, the phenomenal giant magnetoresistance(GMR) effect, which is the novel feature of the currently used multilayered thin film, has already been observed in multilayered nanowire systems at ambient temperature. Geometrical confinement of the supper lattice along the 2-dimensions (2-D) to construct the 1-D multilayered nanowire prohibits the minimization of magnetic interaction- offering a rich variety of magnetic properties in nanowire that can be exploited for novel functionality. In addition, introduction of non-magnetic spacer between the magnetic layers presents additional advantage in controlling magnetic properties via tuning the interlayer magnetic interaction. Despite of a large volume of theoretical works devoted towards the understanding of GMR and IEC in super lattice structures, limited theoretical calculations are reported in 1-D multilayered systems. Thus to gauge their potential application in new generation magneto-electronic devices, in this thesis, I have discussed the usage of first principles density functional theory (DFT) in predicting the equilibrium structure, stability as well as electronic and magnetic properties of one dimensional multilayered nanowires. Particularly, I have focused on the electronic and magnetic properties of Fe/Pt multilayered nanowire structures and the role of non-magnetic Pt spacer in modulating the magnetic properties of the wire. It is found that the average magnetic moment per atom in the nanowire increases monotonically with an ~1/(N(Fe)) dependance, where N(Fe) is the number of iron layers in the nanowire. A simple model based upon the interfacial structure is given to explain the 1/(N(Fe)) trend in magnetic moment obtained from the first principle calculations. A new mechanism, based upon spin flip with in the layer and multistep electron transfer between the layers, is proposed to elucidate the enhancement of magnetic moment of Iron atom at the Platinum interface. The calculated IEC in the Fe/Pt multilayered nanowire is found to switch sign as the width of the non-magnetic spacer varies. The competition among short and long range direct exchange and the super exchange has been found to play a key role for the non-monotonous sign in IEC depending upon the width of the Platinum spacer layer. The calculated magnetoresistance from Julliere's model also exhibit similar switching behavior as that of IEC. The universality of the behavior of exchange coupling has also been looked into by introducing different non-magnetic spacers like Palladium, Copper, Silver, and Gold in between magnetic Iron layers. The nature of hybridization between Fe and other non-magnetic spacer is found to dictate the inter layer magnetic interaction. For example, in Fe/Pd nanowire the d-p hybridization in two spacer layer case favors anti-ferromagnetic (AFM) configuration over ferromagnetic (FM) configuration. However, the hybridization between half-filled Fe(d) and filled Cu(p) state in Fe/Cu nanowire favors FM coupling in the 2-spacer system.

First principles study of Bi dopen CdTe thin film solar cells: electronic and optical properties

Nowadays, efficiency improvement of solar cells is one of the most important issues in photovoltaic systems and CdTe is one of the most promising thin film photovoltaic materials we can found. CdTe reported efficiencies in solar energy conversion have been as good as that found in polycrystalline Si thin film cell [1], besides CdTe can be easily produced at industrial scale.

Optical and structural properties of InAlN/GaN Bragg reflectors examined by transmission electron microscopy and electron energy loss spectroscopy

Molecular beam epitaxy growth of ten-period lattice-matched InAlN/GaN distributed Bragg reflectors (DBRs) with peak reflectivity centered around 400nm is reported including optical and transmission electron microscopy (TEM) measurements [1]. Good periodicity heterostructures with crack-free surfaces were confirmed, but, also a significant residual optical absorption below the bandgap was measured. The TEM characterization ascribes the origin of this problem to polymorfism and planar defects in the GaN layers and to the existence of an In-rich layer at the InAlN/GaN interfaces. In this work, several TEM based techniques have been combined.

Electronic and optical properties of substitutional V, Cr and Ir impurities in Cu2ZnSnS4

The substitution of cation atoms by V, Cr and It in the natural and synthetic quaternary Cu2ZnSnS4 semiconductor is analyzed using first-principles methods. In most of the substitutions, the electronic structure of these modified CZTS is characterized for intermediate bands with different occupation and position within of the energy band gap. A study of the symmetry and composition of these intermediate bands is carried out for all substitutions. These bands permit additional photon absorption and emission channels depending on their occupation. The optical properties are obtained and analyzed. The absorption coefficients are split into contributions from the different absorption channels and from the inter- and intra-atomic components. The sub bandgap transitions are significant in many cases because the anion states contribute to the valence, conduction and intermediates bands. These properties could therefore be used for novel optoelectronic devices.

The nitrite reductase from Pseudomonas aeruginosa: Essential role of two active-site histidines in the catalytic and structural properties

Cd1 nitrite reductase catalyzes the conversion of nitrite to NO in denitrifying bacteria. Reduction of the substrate occurs at the d1-heme site, which faces on the distal side some residues thought to be essential for substrate binding and catalysis. We report the results obtained by mutating to Ala the two invariant active site histidines, His-327 and His-369, of the enzyme from Pseudomonas aeruginosa. Both mutants have lost nitrite reductase activity but maintain the ability to reduce O2 to water. Nitrite reductase activity is impaired because of the accumulation of a catalytically inactive form, possibly because the productive displacement of NO from the ferric d1-heme iron is impaired. Moreover, the two distal His play different roles in catalysis; His-369 is absolutely essential for the stability of the Michaelis complex. The structures of both mutants show (i) the new side chain in the active site, (ii) a loss of density of Tyr-10, which slipped away with the N-terminal arm, and (iii) a large topological change in the whole c-heme domain, which is displaced 20 Å from the position occupied in the wild-type enzyme. We conclude that the two invariant His play a crucial role in the activity and the structural organization of cd1 nitrite reductase from P. aeruginosa.

Thermodynamic, surface and structural properties of liquid Co-Si alloys

The knowledge of thermophysical properties of liquid Co-Si alloys is a key requirement for manufacturing of composite materials by infiltration method. Despite this need, the experimental and predicted property data of the Co-Si system are scarce and often inconsistent between the various sources. In the present work the mixing behaviour of Co-Si melts has been analysed through the study of the concentration dependence of various thermodynamic, surface (surface tension and surface composition) and structural properties (concentration fluctuations in the long-wavelength limit and chemical short-range order parameter) in the framework of the Compound Formation Model (CFM) and Quasi Chemical Approximation for regular solutions (QCA). In addition, the surface tension of the Co22·5Si77.5 (in at%) eutectic alloy, that is proposed to be used as the infiltrant, has been measured by the pendant drop method at temperatures ranging from 1593 to 1773 K. The results obtained were discussed with respect to both, temperature and concentration, and subsequently compared with the model predictions and literature data.

Chemical and structural disorder in eumelanins: A possible explanation for broadband absorbance

We report the results of an experimental and theoretical study of the electronic and structural properties of a key eumelanin precursor-5,6,-dihydroxyindole-2-carboxylic acid ( DHICA) - and its dimeric forms. We have used optical spectroscopy to follow the oxidative polymerization of DHICA to eumelanin and observe red shifting and broadening of the absorption spectrum as the reaction proceeds. First principles density functional theory calculations indicate that DHICA oligomers ( possible reaction products of oxidative polymerization) have the gap between the highest occupied molecular orbital and the lowest unoccupied molecular orbital red-shifted gaps with respect to the monomer. Furthermore, different bonding configurations ( leading to oligomers with different structures) produce a range of gaps. These experimental and theoretical results lend support to the chemical disorder model where the broadband monotonic absorption characteristic of all melanins is a consequence of the superposition of a large number of nonhomogeneously broadened Gaussian transitions associated with each of the components of a melanin ensemble. These results suggest that the traditional model of eumelanin as an amorphous organic semiconductor is not required to explain its optical properties and should be thoroughly reexamined. These results have significant implications for our understanding of the physics, chemistry, and biological function of these important biological macromolecules. Indeed, one may speculate that the robust functionality of melanins in vitro is a direct consequence of its heterogeneity, i.e., chemical disorder is a "low cost" natural resource in these systems

Tuning the Electronic and Chemical Properties of Monolayer MoS2Adsorbed on Transition Metal Substrates

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First-Principles Study of the Electronic and Magnetic Properties of Defects in Carbon Nanostructures

Understanding the magnetic properties of graphenic nanostructures is instrumental in future spintronics applications. These magnetic properties are known to depend crucially on the presence of defects. Here we review our recent theoretical studies using density functional calculations on two types of defects in carbon nanostructures: Substitutional doping with transition metals, and sp$^3$-type defects created by covalent functionalization with organic and inorganic molecules. We focus on such defects because they can be used to create and control magnetism in graphene-based materials. Our main results are summarized as follows: i)Substitutional metal impurities are fully understood using a model based on the hybridization between the $d$ states of the metal atom and the defect levels associated with an unreconstructed D$_{3h}$ carbon vacancy. We identify three different regimes, associated with the occupation of distinct hybridization levels, which determine the magnetic properties obtained with this type of doping; ii) A spin moment of 1.0 $\mu_B$ is always induced by chemical functionalization when a molecule chemisorbs on a graphene layer via a single C-C (or other weakly polar) covalent bond. The magnetic coupling between adsorbates shows a key dependence on the sublattice adsorption site. This effect is similar to that of H adsorption, however, with universal character; iii) The spin moment of substitutional metal impurities can be controlled using strain. In particular, we show that although Ni substitutionals are non-magnetic in flat and unstrained graphene, the magnetism of these defects can be activated by applying either uniaxial strain or curvature to the graphene layer. All these results provide key information about formation and control of defect-induced magnetism in graphene and related materials.

Asymptotic and structural properties of special cases of the Wright function arising in probability theory

This analysis paper presents previously unknown properties of some special cases of the Wright function whose consideration is necessitated by our work on probability theory and the theory of stochastic processes. Specifically, we establish new asymptotic properties of the particular Wright function 1Ψ1(ρ, k; ρ, 0; x) = X∞ n=0 Γ(k + ρn) Γ(ρn) x n n! (|x| < ∞) when the parameter ρ ∈ (−1, 0)∪(0, ∞) and the argument x is real. In the probability theory applications, which are focused on studies of the Poisson-Tweedie mixtures, the parameter k is a non-negative integer. Several representations involving well-known special functions are given for certain particular values of ρ. The asymptotics of 1Ψ1(ρ, k; ρ, 0; x) are obtained under numerous assumptions on the behavior of the arguments k and x when the parameter ρ is both positive and negative. We also provide some integral representations and structural properties involving the ‘reduced’ Wright function 0Ψ1(−−; ρ, 0; x) with ρ ∈ (−1, 0) ∪ (0, ∞), which might be useful for the derivation of new properties of members of the power-variance family of distributions. Some of these imply a reflection principle that connects the functions 0Ψ1(−−;±ρ, 0; ·) and certain Bessel functions. Several asymptotic relationships for both particular cases of this function are also given. A few of these follow under additional constraints from probability theory results which, although previously available, were unknown to analysts.

Influence of alkylphosphonic acid grafting on the electronic and magnetic properties of La2/3Sr1/3MnO3 surfaces

Self-assembled monolayers (SAMs) are highly promising materials for molecular engineering of electronic and spintronics devices thanks to their surface functionalization properties. In this direction, alkylphosphonic acids have been used to functionalize the most common ferromagnetic electrode in organic spintronics: La2/3Sr1/3MnO3 (LSMO). However, a study on the influence of SAMs grafting on LSMO electronic and magnetic properties is still missing. In this letter, we probe the influence of alkylphosphonic acids-based SAMs on the electronic and magnetic properties of the LSMO surface using different spectroscopies. We observe by X-ray photoemission and X-ray absorption that the grafting of the molecules on the LSMO surface induces a reduction of the Mn oxidation state. Ultraviolet photoelectron spectroscopy measurements also show that the LSMO work function can be modified by surface dipoles opening the door to both tune the charge and spin injection efficiencies in organic devices such as organic light-emitting diodes.