Excitation- and power-dependent photoluminescence from oxidized Ge

Wafer/microcrystallites of oxidized Ge with holes/nanoholes synthesized by thermal oxidation strategy from Ge wafer/microcrystallites can convert one wavelength to another. Both oxidized Ge wafer and microcrystallites shows excitation- and power-dependent luminescence. Red-shift is observed as the excitation wavelength is increased, while blue-shift is observed as power density is increased. Over all, blue-green-yellow-orange luminescence is observed depending on the excitation wavelength and the morphology of oxidized Ge. The various defects level associated with germanium-oxygen vacancies in GeO2 and Ge/GeO2 interface are responsible for the excitation-dependent luminescence. Being a light-conversion material, oxidized Ge is expected to find potential applications in solid-state lighting, photovoltaic devices and photocatalysis. (C) 2013 Elsevier B.V. All rights reserved.

Synthesis, photoluminescence and Judd-Ofelt parameters of LiNa3P2O7:Eu3+ orthorhombic microstructures

We report, for the first time, the photoluminescence properties of Eu3+-doped LiNa3P2O7 phosphor, synthesized by a facile solid-state reaction method in air atmosphere. The crystal structure and phase purity of the phosphors were analyzed by X-ray diffraction analysis. Orthorhombic structural morphology was identified by scanning electron microscopy. The phosphate groups in the phosphor were confirmed by Fourier transform infrared analysis. Bandgap of the phosphor was calculated from the diffuse reflectance spectra data using Kubelka-Munk function. Under 395-nm UV excitation, the phosphors show signs of emitting red color due to the D-5(0) -> F-7(2) transition. In accordance with Judd-Ofelt theory, spectroscopic parameters such as oscillator intensity parameter Omega(t) (t = 2), spontaneous emission probabilities, fluorescence branching ratios and radiative lifetimes were calculated and analyzed for the first time in this system.

Bio-inspired route for the synthesis of spherical shaped MgO:Fe3+ nanoparticles: Structural, photoluminescence and photocatalytic investigation

MgO:Fe3+ (0.1-5 mol%) nanoparticles (NPs) were synthesized via eco-friendly, inexpensive and simple low temperature solution combustion route using Aloe vera gel as fuel. The final products were characterized by SEM, TEM and HRTEM. PXRD data and Rietveld analysis revealed the formation of cubic system. The influence of Fe3+ ion concentration on the structure morphology, UV absorption, PL emission and photocatalytic activity of MgO:Fe3+ NPs were investigated. The yellow emission with CIE chromaticity coordinates (0.44, 0.52) and average correlated color temperature value was found to be 3540 K which corresponds to warm light of NPs. The control of Fe3+. on MgO matrix influences the photocatalytic decolorization of methylene blue (MB) under UV light. The enhanced photocatalytic activity of MgO:Fe3+ (4 mol%) was attributed to dopant concentration, effective crystallite size, textural properties, decreased band gap and capability for reducing the electron hole pair recombination. Further, the trends of inhibitory effect in the presence of different radical scavengers were explored. These findings open up new avenues for the exploration of Fe-doped MgO in eco-friendly water applications and in the process of display devices. (C) 2015 Elsevier B.V. All rights reserved.

Synthesis of Eu3+-activated ZnO superstructures: Photoluminescence, Judd-Ofelt analysis and Sunlight photocatalytic properties

Photoluminescence and photocatalytic properties of Eu-doped ZnO nanoparticles (NPs) were synthesized by facile phyto route. XPS results demonstrated the existence of Eu3+ as dopant into ZnO. Morphologies of the NPs were mainly dependent on Eu3+ and Aloe vera gel. Red shift of energy band gap was due to the creation of intermediate energy states of Eu3+ and oxygen vacancies in the band gap. PL emission of ZnO:Eu3+ (1-11 mol%, 8 ml and 7 mol%, 2-12 ml) exhibit characteristic peaks of D-5(0) -> F-7(2) transitions. From the Judd-Ofelt analysis, intensities of transitions between different.' levels dependent on the symmetry of the local environment of Eu3+ ions. CIE chromaticity co-ordinates confirm reddish emission of the phosphor. Further, NPs exhibit excellent photocatalytic activity for the degradation of Rhodamine B (94%) under Sunlight was attributed to crystallite size, band gap, morphology and oxygen vacancies. In addition, photocatalyst reusability studies were conducted and found that Eu-doped catalyst could be reused several times with negligible decrease in catalytic activity. The present work directs new possibilities to provide some new insights into the design of new phyto synthesized nanophosphors for display devices, photocatalysts with high activity for environmental clean-up and solar energy conversion. (C) 2015 Elsevier B.V. All rights reserved.

Ray tracing based path-length calculations for polarized light tomographic imaging

A ray tracing based path length calculation is investigated for polarized light transport in a pixel space. Tomographic imaging using polarized light transport is promising for applications in optical projection tomography of small animal imaging and turbid media with low scattering. Polarized light transport through a medium can have complex effects due to interactions such as optical rotation of linearly polarized light, birefringence, diattenuation and interior refraction. Here we investigate the effects of refraction of polarized light in a non-scattering medium. This step is used to obtain the initial absorption estimate. This estimate can be used as prior in Monte Carlo (MC) program that simulates the transport of polarized light through a scattering medium to assist in faster convergence of the final estimate. The reflectance for p-polarized (parallel) and s-polarized (perpendicular) are different and hence there is a difference in the intensities that reach the detector end. The algorithm computes the length of the ray in each pixel along the refracted path and this is used to build the weight matrix. This weight matrix with corrected ray path length and the resultant intensity reaching the detector for each ray is used in the algebraic reconstruction (ART) method. The proposed method is tested with numerical phantoms for various noise levels. The refraction errors due to regions of different refractive index are discussed, the difference in intensities with polarization is considered. The improvements in reconstruction using the correction so applied is presented. This is achieved by tracking the path of the ray as well as the intensity of the ray as it traverses through the medium.

Synthesis and Photoluminescence Properties of Eu3+ activated Ce0.5Al0.5O2-delta Nanophosphors for WLEDs Application

A series of Eu3+ activated Ce0.5Al0.5O2-delta nanophosphors have been synthesized by the nitrate - citrate gel combustion method. All the compounds crystallized in the cubic fluorite CeO2 structure with space group Fm-3m (No. 225). FESEM revealed the flakes-like morphology. The average particle size was estimated from TEM studies and found to be in the range 15-25 nm. The values were in good agreement with the Scherer's method. In photoluminescence (PL) spectra, the D-5(0) -> F-7(2) (612 nm) transition dominates than other transitions which indicates that the Eu3+ ions occupy a site without inversion center. CIE chromaticity diagram confirmed that these nanophosphors can be useful in the fabrication of red component in white light emitting diodes (WLEDs).

Temperature-Dependent Photoluminescence of g-C3N4: Implication for Temperature Sensing

We report the temperature-dependent photoluminescence (PL) properties of polymeric graphite-like carbon nitride (g-C3N4) and a methodology for the determination of quantum efficiency along with the activation energy. The PL is shown to originate from three different pathways of transitions: sigma*-LP, pi*-LP, and pi*-pi, respectively. The overall activation energy is found to be similar to 73.58 meV which is much lower than the exciton binding energy reported theoretically but ideal for highly sensitive wide-range temperature sensing. The quantum yield derived from the PL data is 23.3%, whereas the absolute quantum yield is 5.3%. We propose that the temperature-dependent PL can be exploited for the evaluation of the temperature dependency of quantum yield as well as for temperature sensing. Our analysis further indicates that g-C3N4 is well-suited for wide-range temperature sensing.

Development of a spin polarized low energy electron diffraction system

We have designed and constructed a spin polarized low energy electron diffraction system working in the reflected electron pulse counting mode. This system is capable of measuring asymmetries due to spin-orbit and exchange interactions. Photoemission from a strained GaAs/GaAsP super lattice is used as the source of spin polarized electrons. Spin-orbit asymmetry is evaluated for Ir(100) single crystal at various energies. Subsequently, exchange asymmetry has been evaluated on 40 monolayer Fe deposited on Ir(100). This instrument proves to be useful in understanding structure and magnetism at surfaces. (C) 2016 AIP Publishing LLC.

Size and temperature dependence of the photoluminescence properties of NIR emitting ternary alloyed mercury cadmium telluride quantum dots

Exciton-phonon coupling and nonradiative relaxation processes have been investigated in near-infrared (NIR) emitting ternary alloyed mercury cadmium telluride (CdHgTe) quantum dots. Organically capped CdHgTe nanocrystals of sizes varying from 2.5-4.2 nm have been synthesized where emission is in the NIR region of 650-855 nm. Temperature-dependent (15-300 K) photoluminescence (PL) and the decay dynamics of PL at 300 K have been studied to understand the photophysical properties. The PL decay kinetics shows the transition from triexponential to biexponential on increasing the size of the quantom dots (QDs), informing the change in the distribution of the emitting states. The energy gap is found to be following the Varshni relation with a temperature coefficient of 2.1-2.8 x 10(-4) eV K-1. The strength of the electron-phonon coupling, which is reflected in the Huang and Rhys factor S, is found in the range of 1.17-1.68 for QDs with a size of 2.5-4.2 nm. The integrated PL intensity is nearly constant until 50 K, and slowly decreases up to 140 K, beyond which it decreases at a faster rate. The mechanism for PL quenching with temperature is attributed to the presence of nonradiative relaxation channels, where the excited carriers are thermally stimulated to the surface defect/trap states. At temperatures of different region (<140 K and 140-300 K), traps of low (13-25 meV) and high (65-140 meV) activation energies seem to be controlling the quenching of the PL emission. The broadening of emission linewidth is found to due to exciton-acoustic phonon scattering and exciton-longitudinal optical (LO) phonon coupling. The exciton-acoustic phonon scattering coefficient is found to be enhanced up to 55 MU eV K-1 due to a stronger confinement effect. These findings give insight into understanding the photophysical properties of CdHgTe QDs and pave the way for their possible applications in the fields of NIR photodetectors and other optoelectronic devices.

Observation of Size-Dependent Electron-Phonon Scattering and Temperature-Dependent Photoluminescence Quenching in Triangular-Shaped Silver Nanoparticles

Research studies on plasmonic properties of triangular-shaped silver nanoparticles might lead to several interesting applications. However, in this work, triangular-shaped silver nanoparticles have been synthesized by simple solvothermal technique and reported the effect of size on the electron-phonon scattering in the synthesized materials by analyzing their temperature-dependent photoluminescence (PL) emission characteristics. It has been observed that total integrated PL emission intensity is quenched by 33 % with the increase in temperature from 278 to 323 K. The observed decrease in PL emission intensity has been ascribed to the increase of electron-phonon scattering rate with the increase in temperature. The values of electron-phonon coupling strength (S) for synthesized samples have been evaluated by theoretical fitting of the experimentally obtained PL emission data. Smaller sized triangular nanoparticle has been found to exhibit stronger temperature dependence in PL emission, which strongly suggests that smaller sized triangular silver nanostructures have better electron-phonon coupling.

Tuning Photoluminescence Response by Electric Field in Electrically Soft Ferroelectrics

We show that an electrically soft ferroelectric host can be used to tune the photoluminescence (PL) response of rare-earth emitter ions by external electric field. The proof of this concept is demonstrated by changing the PL response of the Eu3+ ion by electric field on a model system Eu-doped 0.94(Na1/2Bi1/2TiO3)-0.06(BaTiO3). We also show that new channels of radiative transitions, forbidden otherwise, open up due to positional disorder in the system, which can as well be tuned by electric field.

Spin populations in one-dimensional alternant spin systems: A theoretical approach

Spin-density maps, deduced from polarized neutron diffraction experiments, for both the pair and chain compounds of the system Mn2+Cu2+ have been reported recently. These results have motivated us to investigate theoretically the spin populations in such alternant mixed-spin systems. In this paper, we report our studies on the one-dimensional ferrimagnetic systems (S-A,S-B)(N) where hi is the number of AB pairs. We have considered all cases in which the spin Sri takes on allowed values in the range I to 7/2 while the spin S-B is held fixed at 1/2. The theoretical studies have been carried out on the isotropic Heisenberg model, using the density matrix renormalization group method. The effect of the magnitude of the larger spin SA On the quantum fluctuations in both A and B sublattices has been studied as a function of the system size N. We have investigated systems with both periodic and open boundary conditions, the latter with a view to understanding end-of-chain effects. The spin populations have been followed as a function of temperature as well as an applied magnetic field. High-magnetic fields are found to lead to interesting re-entrant behavior. The ratio of spin populations P-A-P-B is not sensitive to temperature at low temperatures.

A New Class Of Photo-Cross-Linkable Side-Chain Liquid Crystalline Polymers Containing Bis(Benzylidene)Cyclohexanone Units

This paper reports a new class of photo-cross-linkable side chain liquid crystalline polymers (PSCLCPs) based on the bis(benzylidene)cyclohexanone unit, which functions as both a mesogen and a photoactive center. Polymers with the bis(benzylidene)cyclohexanone unit and varying spacer length have been synthesized. Copolymers of bis(benzylidene)cyclohexanone containing monomer and cholesterol benzoate containing monomer with different compositions have also been prepared. All these polymers have been structurally characterized by spectroscopic techniques. Thermal transitions were studied by DSC, and mesophases were identified by polarized light optical microscopy (POM). The intermediate compounds OH-x, the monomers SCLCM-x, and the corresponding polymers PSCLCP-x, which are essentially based on bis(benzylidene)cyclohexanone, all show a nematic mesophase. Transition temperatures were observed to decrease with increasing spacer length. The copolymers with varying compositions exhibit a cholesteric mesophase, and the transition temperatures increase with the cholesteric benzoate units in the copolymer. Photolysis of the low molecular weight liquid crystalline bis(benzylidene)-cyclohexanone compound reveals that there are two kinds of photoreactions in these systems: the EZ photoisomerization and 2 pi + 2 pi addition. The EZ photoisomerization in the LC phase disrupts the parallel stacking of the mesogens, resulting in the transition from the LC phase to the isotropic phase. The photoreaction involving the 2 pi + 2 pi addition of the bis(benzylidene)cyclohexanone units in the polymer results in the cross-linking of the chains. The liquid crystalline induced circular dichroism (LCICD) studies of the cholesterol benzoate copolymers revealed that the cholesteric supramolecular order remains even after the photo-cross-linking.

Synthesis and properties of main chain discotic liquid crystalline polyethers based on rufigallol

Two series of thermotropic main chain discotic liquid crystalline polyethers, PR4m-n, based on rufigallol were prepared starting from the symmetric tetraethers of rufigallol, R4m; m and n represent the number of carbon atoms in the side chain and spacer segment, respectively. The symmetric tetraethers were in turn readily prepared by selective alkylation of rufigallol under controlled phase-transfer conditions. GPC analysis of the polymers suggested that they were all of moderate molecular weights, with M-n varying between 5400 and 17 000. The length of the spacer segment n in these polyethers was systematically varied, and its effect on the phase transition temperatures and the mesophase structure was examined using DSC, polarized light microscopy, and X-ray diffraction. It is noticed that when the spacer lengths are relatively long(n greater than or equal to 2m), the isotropization temperature (TD-i) decreases as the spacer length n increases, an observation that is in accordance with those previously made. However, when the spacer lengths are relatively small (n < 2m), the dependence of TD-i is quite the opposite; TD-i actually increases with an increase in spacer length. Furthermore, X-ray diffraction studies indicate that, in the discotic columnar mesophases that are formed, the columns pack in a hexagonal manner when n greater than or equal to 2m, while they do so in a rectangular lattice when n < 2m, leading to the formation of Dh and Dr mesophases, respectively. Finally, comparison of the discotic polyethers with their low molar mass analogues confirms the role of polymerization in stabilizing the mesophase; while all the polymers exhibit columnar mesophases, some of their low molar mass analogues are not liquid crystalline.

Synthesis of novel poly[(2,5-dimethoxy-p-phenylene)vinylene] precursors having two eliminatable groups: An approach for the control of conjugation length

Poly[(2,5-dimethoxy-p-phenylene)vinylene] (DMPPV) of varying conjugation length was synthesized by selective elimination of organic soluble precursor polymers that contained two eliminatable groups, namely, methoxy and acetate groups. These precursor copolymers were in turn synthesized by competitive nucleophilic substitution of the sulfonium polyelectrolyte precursor (generated by the standard Wessling route) using methanol and sodium acetate in acetic acid. The composition of the precursor copolymer, in terms of the relative amounts of methoxy and acetate groups, was controlled by varying the composition of the reaction mixture during nucleophilic substitution. Thermal elimination of these precursor copolymers at 250 degrees C, yielded partially conjugated polymers, whose color varied from light yellow to deep red. FT-IR studies confirmed that, while essentially all the acetate groups were eliminated, the methoxy groups were intact and caused the interruption in conjugation. Preliminary photoluminescence studies of the partially eliminated DMPPV samples showed a gradual shift in the emission maximum from 498 to 598 nm with increasing conjugation lengths, suggesting that the color of LED devices fabricated from such polymers can, in principle, be fine-tuned.