Resonant energy transfer among naturally available bio materials for white light emission.

In this work we have studied the fluorescence of natural dyes and generated nearly pure white light with chromaticity intensity (CIE) coordinate (0.35,0.35). The colour rendering index (CRI) and colour temperature corresponding to the CIE coordinate are calculated and these dyes are ideal for cool white light emission. It was observed that a broadband and simultaneous emission involving anthocyanin and polyphenol ellergic acid from jamun, curcumin and chlorophyll from spinach leaves played a vital role in obtaining a CIE index close to that of pure white light. The white light emission is due to the Förster resonance energy transfer (FRET) from curcumin to anthocyanin and ellergic acid to curcumin. Efficiency of FRET is calculated and different possibilities studied. For the polyphenol ellergic acid, curcumin FRET pair the spectral overlap integral and the efficiency are 3.29 × 10-24 m2, 99.97% and for the curcumin, anthocyanin pair, they are 4.03 × 10-24 m2, 76%, respectively.

Spectroscopic analysis of Eu3+ doped silica-titania-polydimethylsiloxane hybrid ORMOSILs.

Eu3+ doped silica-titania-polydimethylsiloxane hybrid ORMOSILs were synthesized via a non-hydrolytic sol-gel route. The structural and thermal analyses of the samples confirmed that the matrix structure remains unaffected by doping with different concentrations of Eu3+ ions. Photoluminescence (PL) studies performed at 394 nm on Eu3+ doped ORMOSILs imply that they emit broad blue host emission and the characteristic Eu3+ red emissions simultaneously. Also, the samples were excited at the charge transfer (CT) band and this confirmed the existence of an energy transfer path from the host to the Eu3+ ions via Ti4+-O2--Eu3+ bonds. The phonon energy of the host matrix was estimated by phonon sideband (PSB) analysis and the results were substantiated by Raman analysis. Judd-Ofelt (JO) parameters were also evaluated which give details about the local surroundings of the Eu3+ ions in the system and these parameters were further used for predicting the radiative properties of 5D0 → 7F1,2,4 transitions of Eu3+ ions. Furthermore, the quantum efficiency and CIE co-ordinates were evaluated and it was found that Eu3+ doped silica-titania-polydimethylsiloxane ORMOSIL has an intense pinkish red emission with a quantum efficiency of 30.7%.

Structural and spectroscopic investigations on the quenching free luminescence of europium oxalate nanocrystals.

The structural features leading to the intense quenching free luminescence exhibited by europium oxalate nanocrystals, poly[[hexaaquatri-µ2-oxalato-dieuropium] 4.34-hydrate], {[Eu2(C2O4)3(H2O)6]·4.34H2O}n, is the focal point of this report. Europium oxalate nanocrystals were synthesized by a simple microwave-assisted co-precipitation method. Powder X-ray diffraction analysis revealed the monoclinic structure of the nanocrystals and the phase purity. The morphology and particle size were examined by transmission electron microscopy (TEM) analysis. Luminescence measurements on a series of samples of La2-xEux(C2O4)3·10H2O, with x varying in the range 0.1 to 2, established the quenching free nature exhibited by the europium oxalate nanocrystals. A single-crystal structure analysis was carried out and the quenching free luminescence is explained on the basis of the crystal structure. A detailed photoluminescence characterization was carried out using excitation and emission studies, decay analysis, and CIE coordinate and colour purity evaluation. The various spectroscopic parameters were evaluated by Judd-Ofelt theoretical analysis and the results are discussed on the basis of the crystal structure analysis.

Development of Thick Superhydrophilic TiO2-ZrO2 Transparent Coatings Realized through the Inclusion of Poly(methyl methacrylate) and Pluronic-F127.

A thick coating of hierarchically porous double-templated TiO2-ZrO2-PMMA-PF127 with excellent self-cleaning properties and high transmittance has been developed for the first time on glass substrates using a simple dip-coating technique. Comparative studies of this sample with a thick and transparent coating of single-templated TiO2-ZrO2-PMMA have been performed to probe the origin of its exceptional properties. The formation of the composites, successful incorporation of the polymer into the matrix, and the porous nature of the films have been studied. The presence of Ti2+ in the double-templated samples has been confirmed, which suggest the chemisorption of water on the surface of the film. The variation in the self-cleaning properties of the samples on UV-illumination has also been studied. The double-templated film is found to possess the capability of good hydrophilic retention even 2 days after UV-irradiation.

High temperature ferroelectric behaviour in α-MnO2 nanorods realised through enriched oxygen vacancy induced non-stoichiometry.

Nanostructuring followed by incorporation of defect induced non-stoichiometry is an emerging field of prominence due to its capacity to introduce unprecedented properties in materials with potential applications. In this work, crystalline α-MnO2 nanorods are synthesised using a facile co-precipitation method to exhibit ferroelectric behaviour for the first time. The evolution mechanism of the nanorods is investigated using XRD, HRTEM and FTIR spectra, while their thermal stability is probed using TGA/DTA. The novel properties observed are the result of structural rearrangements sparked by electrons in mixed valence cations (Mn3+/Mn4+). The high density of Jahn-Teller active Mn3+ cations breaks the inversion symmetry in α-MnO2, thereby altering the atomic environment inducing distortion in the basic MnO6 octahedra. Since variable temperature XRD analysis confirms the phase stability of the crystal structure up to very high temperatures, the ferroelectric phase exhibited by the material below Tc is an outcome of the combined effects of orbital ordering (OO) of the eg electron in Mn3+ and charge ordering (CO) of Mn3+ and Mn4+ cations. This is confirmed by DSC analysis. The breakdown of the ferroelectric nature is identified to originate as a result of octahedral tilting as suggested by temperature-dependent Raman studies. Magnetic and electrical transport studies provide additional evidence of a CO ferroelectric phase as they predict the existence of double-exchange hopping conduction and surface ferromagnetism in the sample.

Optical analysis of samarium doped sodium bismuth silicate glass.

Samarium doped sodium bismuth silicate glass was synthesized using the melt quenching method. Detailed optical spectroscopic studies of the glassy material were carried out in the UV-Vis-NIR spectral range. Using the optical absorption spectra Judd-Ofelt (JO) parameters are derived. The calculated values of the JO parameters are utilized in evaluating the various radiative parameters such as electric dipole line strengths (Sed), radiative transition probabilities (Arad), radiative lifetimes (τrad), fluorescence branching ratios (ß) and the integrated absorption cross- sections (σa) for stimulated emission from various excited states of Sm3+‡ ion. The principal fluorescence transitions are identified by recording the fluorescence spectrum. Our analysis revealed that the novel glassy system has the optimum values for the key parameters viz. spectroscopic quality factor, optical gain, stimulated emission cross section and quantum efficiency, which are required for a high performance optical amplifier. Calculated chromaticity co-ordinates (0.61, 0.38) also confirm its application potential in display devices.

NIR emission studies and dielectric properties of Er(3+)-doped multicomponent tellurite glasses.

Multicomponent tellurite glasses containing altered concentrations of Er2O3 (ranging from 0 to 1 mol%) were prepared by the standard melt quenching technique. Investigations through energy dispersive X-ray spectroscopy (EDS), Raman scattering spectroscopy, Fourier transform infrared (FTIR) spectroscopy, near-infrared (NIR) emission studies and dielectric measurement techniques were done to probe their compositional, structural, spectroscopic and dielectric characteristics. The broad emission together with the high values of the effective linewidth (~63 nm), stimulated emission cross-section (9.67 × 10(-21) cm(2)) and lifetime (2.56 ms) of (4)I13/2 level for 0.5 mol% of Er(3+) makes these glasses attractive for broadband amplifiers. From the measured capacitance and dissipation factor, the relative permittivity, dielectric loss and the conductivity were computed; which furnish the dielectric nature of the multicomponent tellurite glasses that depend on the applied frequency. Assuming the ideal Debye behavior as substantiated by Cole-Cole plot, an examination of the real and imaginary parts of impedance was performed. The power-law and Cole-Cole parameters were resolved for all the glass samples. From the assessment of the emission analysis and dielectric properties of the glass samples, it was obvious that the Er(3+) ion concentration had played a vital role in tuning the optical and dielectric properties and the 0.5 mol% of Er(3+) -doped glass was confirmed as the optimum composition.

Evidence for enhanced optical properties through plasmon resonance energy transfer in silver silica nanocomposites.

Silver nanoparticles were dispersed in the pores of monolithic mesoporous silica prepared by a modified sol-gel method. Structural and microstructural analyses were carried out by Fourier transform infrared spectroscopy and transmission electron microscopy. X-ray photoelectron spectroscopy was employed to determine the chemical states of silver in the silica matrix. Optical absorption studies show the evolution absorption band around 300 nm for silver (Ag) in a silica matrix and it was found to be redshifted to 422 nm on annealing. Photoluminescence studies indicate the presence of various luminescent emitting centers corresponding to silver ions and silver dimers in the SiO2 matrix. The enhancement of absorption and photoluminescence properties is attributed to plasmon resonance energy transfer from Ag nanoparticles to luminescent species in the matrix.

Spectroscopic and photoluminescence characterization of Dy(3+) in Sr0.5Ca0.5TiO3 phosphor.

The spectroscopic and photoluminescence characteristics of trivalent dysprosium (Dy(3+))-doped Sr0.5Ca0.5TiO3 phosphor materials synthesized via solid-state reaction method were studied. The X-ray diffraction profile confirmed the orthorhombic perovskite structure of the prepared samples. Judd-Ofelt analysis was carried out to obtain the intensity parameters and predicted radiative properties of Sr0.5Ca0.5TiO3:2wt%Dy(3+). The photoluminescence spectrum of Dy(3+)-doped Sr0.5Ca0.5TiO3 showed three emission peaks at 481, 574 and 638 nm corresponding to (4)F9/2 →(6)H15/2, (4)F9/2 →(6)H13/2 and (4)F9/2 →(6)H11/2 transitions respectively. The variation of luminescence intensity with different excitation wavelengths and Dy(3+) concentrations is discussed. The decay profiles of (4)F9/2 excited levels of Dy(3+) ions show bi-exponential behaviour and also a decrease in average lifetime with increase in Dy(3+) concentration. Yellow to blue luminescence intensity ratio, CIE chromaticity co-ordinates and correlated color temperature were also calculated for different concentrations of Dy(3+)-doped Sr0.5Ca0.5TiO3 phosphor at different λex.

Synthesis and luminescence characterization of Sr(0.5)Ca(0.5)TiO3:Sm(3+) phosphor.

The spectroscopic properties of trivalent samarium doped Sr0.5Ca0.5TiO3 perovskite phosphor material (Sr0.5Ca0.5TiO3:xSm(3+), x=0.05, 0.1, 0.5, 1, 1.5) synthesized by the solid state method have been studied. The X-Ray Diffraction profile confirms the orthorhombic perovskite Sr0.5Ca0.5TiO3 structure of the prepared samples. The SEM study reveals the surface morphology. The Judd-Ofelt intensity parameters were calculated for 0.5 wt% Sm(3+) doped Sr0.5Ca0.5TiO3. Transition probabilities, branching ratios and radiative lifetime were evaluated by using Judd-Ofelt analysis. The emission spectra under 405 nm excitation shows five emission peaks at 564 nm, 599 nm, 645 nm, 707 nm and 776 nm corresponding to the transitions (4)G5/2→(6)Hj (j=5/2, 7/2, 9/2, 11/2 and 13/2) respectively. The higher values of branching ratio and stimulated emission cross-section for (4)G5/2→(6)H7/2 transition of Sr0.5Ca0.5TiO3:0.5 wt% Sm(3+) shows its suitability in the field of visible lasers and optical fiber amplifiers. The experimental lifetimes of Sm(3+) doped samples were estimated using the decay curves corresponding to (4)G5/2→(6)H7/2 transition upon 405 nm excitation. Concentration dependence on emission intensity and experimental lifetime were also studied. From the CIE diagram we can see that as the concentration of Sm(3+) ions increases from 0.05 wt% to 1.5 wt% the CIE color co-ordinates changes from greenish yellow to yellowish orange.

Investigations on spectroscopic properties of Er(3+)-doped Li-Zn fluoroborate glass.

Er(3+)-doped Li-Zn fluoroborate glass was synthesized via melt quenching technique. Optical properties of the glass were investigated by UV-Vis-NIR absorption and emission spectra. To evaluate the nature of Er(3+)-ligand bond in the glass network, nephelauxetic ratios and bonding parameter were calculated. Judd-Ofelt analysis and hence the radiative properties of the present glass system were evaluated for ascertaining the suitability of the glass for laser applications and compared those with the emission spectra. Absorption cross-sections have been calculated from the absorption spectrum and stimulated emission cross-sections were estimated using McCumber theory for (4)I13/2↔(4)I15/2 transitions. The results of the present glass were compared with those obtained for some other Er(3+)-doped glass systems.

Structural and spectral investigation of terbium molybdate nanophosphor.

Terbium molybdate nanophosphors were synthesized through a facile sol-gel route. The structure of the phosphors was characterized by X-ray diffraction, Raman spectra and Fourier transform infrared spectroscopy analysis. The X-ray diffraction studies revealed that the structure of the nanophosphor gradually changes from monoclinic to orthorhombic phase as heated from 700 to 900 °C. High resolution transmission electron microscopy, SAED and EDS were also employed to characterize the size, crystallinity and composition of the samples. Detailed spectroscopic investigations were carried out by Judd-Ofelt analysis based on UV-Visible-NIR absorption and emission spectra. The luminescence spectra suggest that phosphors with orthorhombic structure have better luminescence properties than the monoclinic structure. The phosphors showed intense green emission under near-UV excitation due to the energy transfer from the host lattice to Tb(3+) ions. The CIE coordinates suggest enhanced color purity for green emission and short fluorescence decay values proposes the suitability for LED applications. These phosphors can be applied as promising candidates for blue and near-UV excited WLEDs.

Synthesis and luminescence characterization of Pr(3+) doped Sr1.5Ca0.5SiO4 phosphor.

Luminescence properties of Pr(3+) activated Sr1.5Ca0.5SiO4 phosphors synthesized by solid state reaction method are reported in this work. Blue, orange red and red emissions were observed in the Pr(3+) doped sample under 444nm excitation and these emissions are assigned as (3)P0→(3)H4, (3)P0→(3)H6 and (3)P0→(3)F4 transitions. The emission intensity shows a maximum corresponding to the 0.5wt% Pr(3+) ion. The decay analysis was done for 0.05 and 0.5wt% Pr(3+) doped samples for the transition (3)P0→(3)H6. The life times of 0.05 and 0.5wt% Pr(3+) doped samples were calculated by fitting to exponential and non-exponential curve respectively, and are found to be 156 and 105µs respectively. The non-exponential behaviour arises due to the statistical distribution of the distances between the ground state Pr(3+) ions and excited state Pr(3+) ions, which cause the inhomogeneous energy transfer rate. The XRD spectrum confirmed the triclinic phase of the prepared phosphors. The compositions of the samples were determined by the energy dispersive X-ray spectra. From the SEM images it is observed that the particles are agglomerated and are irregularly shaped. IR absorption bands were assigned to different vibrational modes. The well resolved peaks shown in the absorption spectra are identical to the excitation spectra of the phosphor samples. Pr(3+) activated Sr1.5Ca0.5SiO4 phosphors can be efficiently excited with 444nm irradiation and emit multicolour visible emissions. From the CIE diagram it can be seen that the prepared phosphor samples give yellowish-green emission.

Structural, spectroscopic and electrical studies of nanostructured porous ZnO thin films prepared by pulsed laser deposition.

ZnO thin films are grown on quartz substrates at various substrate temperatures (ranging from 573 to 973 K) under an oxygen ambience of 0.02 mbar by using pulsed laser ablation. Influence of substrate temperature on the structural, morphological, optical and electrical properties of the ZnO thin films are investigated. The XRD and micro-Raman spectra reveal the presence of hexagonal wurtzite structure of ZnO with preferred orientation (002). The particle size is calculated using Debye-Scherer equation and the average size of the crystallites are found to be in the range 17-29 nm. The AFM study reveals that the surface morphology of the film depends strongly on the substrate temperature. UV-Visible transmittance spectra show highly transparent nature of the films in visible region. The calculated optical band gap energy is found to be decrease with increase in substrate temperatures. The complex dielectric constant, the loss factor and the distribution of the volume and surface energy loss of the ZnO thin films prepared at different substrate temperatures are calculated. All the films are found to be highly porous in nature. The PL spectra show very strong emission in the blue region for all the films. The dc electrical resistivity of the film decreases with increase in substrate temperature. The temperature dependent electrical measurements done on the film prepared at substrate temperature 573 K reveals that the electric conduction is thermally activated and the activation energy is found to be 0.03911 eV which is less than the reported values for ZnO films.

Synthesis, structural and spectroscopic investigations of nanostructured samarium oxalate crystals.

Nanostructured samarium oxalate crystals were prepared via microwave assisted co-precipitation method. The crystal structure and morphology of the sample were analyzed using X-ray powder diffraction, Scanning electron microscopy and Transmission electron microscopy. The presence of functional groups is ascertained by Fourier transform infrared spectroscopy. Samarium oxalate nanocrystals of average size 20 nm were aggregated together to form nano-plate structure in sub-microrange. Detailed spectroscopic investigation of the prepared phosphor material was carried out by Judd-Ofelt analysis based on the UV-Visible-NIR absorption spectra and photoluminescence emission spectra. The analysis reveals that the transition from energy level (4)G5/2 to (6)H7/2 of Sm(3+) ion has maximum branching ratio and the corresponding orange emission can be used for display applications.

Self-assembly of Silver Nanoparticles and Multiwall Carbon Nanotubes on Decomposed GaAs Surfaces.

Atomic Force Microscopy complemented by Photoluminescence and Reflection High Energy Electron Diffraction has been used to study self-assembly of silver nanoparticles and multiwall carbon nanotubes on thermally decomposed GaAs (100) surfaces. It has been shown that the decomposition leads to the formation of arsenic plate-like structures. Multiwall carbon nanotubes spin coated on the decomposed surfaces were mostly found to occupy the depressions between the plates and formed boundaries. While direct casting of silver nanoparticles is found to induce microdroplets. Annealing at 300°C was observed to contract the microdroplets into combined structures consisting of silver spots surrounded by silver rings. Moreover, casting of colloidal suspension consists of multiwall carbon nanotubes and silver nanoparticles is observed to cause the formation of 2D compact islands. Depending on the multiwall carbon nanotubes diameter, GaAs/multiwall carbon nanotubes/silver system exhibited photoluminescence with varying strength. Such assembly provides a possible bottom up facile way of roughness controlled fabrication of plasmonic systems on GaAs surfaces.

Molecular dynamics simulations of xDNA.

xDNA is a modified DNA, which contains natural as well as expanded bases. Expanded bases are generated by the addition of a benzene spacer to the natural bases. A set of AMBER force-field parameters were derived for the expanded bases and the structural dynamics of the xDNA decamer (xT5' G xT A xC xG C xA xG T3').(xA5' C T xG C G xT A xC A3') was explored using a 22 ns molecular dynamics simulation in explicit solvent. During the simulation, the duplex retained its Watson-Crick base-pairing and double helical structure, with deviations from the starting B-form geometry towards A-form; the deviations are mainly in the backbone torsion angles and in the helical parameters. The sugar pucker of the residues were distributed among a variety of modes; C2' endo, C1' exo, O4' endo, C4' exo, C2' exo, and C3' endo. The enhanced stacking interactions on account of the modification in the bases could help to retain the duplex nature of the helix with minor deviations from the ideal geometry. In our simulation, the xDNA showed a reduced minor groove width and an enlarged major groove width in comparison with the NMR structure. Both the grooves are larger than that of standard B-DNA, but major groove width is larger than that of A-DNA with almost equal minor groove width. The enlarged groove widths and the possibility of additional hydration in the grooves makes xDNA a potential molecule for various applications.

Fluorescence enhancement in Tb3+/CdS nanoparticles doped silica xerogels.

Cadmium sulfide semiconductor nanoparticles along with terbium ions were incorporated in silica xerogels through sol-gel route. The optical absorption and emission spectra confirmed the formation of CdS nanoparticles along with terbium ions in the silica gel. The optical bandgap and size of the CdS nanoparticle were calculated from the absorption spectrum. The TEM measurement was also used to evaluate the average size of the CdS nanoparticles. The fluorescence spectra reveal that the intensity of characteristic emission of terbium ions increases considerably in the presence of CdS nanoparticles even in the gel stage itself and this avoids the need of heating gels at high temperatures. The branching ratios were calculated from the emission spectra using the standard procedure.

2-[2-Benzoyl-3,3-bis-(methyl-sulfan-yl)prop-2-enyl-idene]malononitrile.

The title compound, C(15)H(12)N(2)OS(2), is an example of a push-pull butadiene in which the electron-releasing methyl-sulfanyl groups and electron-withdrawing nitrile groups on either end of the butadiene chain enhance the conjugation in the system. Short intra-molecular C-H⋯S inter-actions are observed. In the crystal structure, an O⋯C short contact of 2.917 (3) Šis observed.

2-[2-(4-Methyl-benzo-yl)-3,3-bis-(methyl-sulfan-yl)prop-2-enyl-idene]malononitrile.

The title compound, C(16)H(14)N(2)OS(2), is an example of a push-pull butadiene in which the electron-releasing and electron-withdrawing attachments on either end of the butadiene chain enhance the conjugation in the system. The mol-ecules are linked by inter-molecular C-H⋯N inter-actions.