Thermal oxidation strategy for the synthesis of phase-controlled GeO2 and photoluminescence characterization

We report the synthesis of trigonal and tetragonal phase GeO2 films/microrods from a Ge wafer/powder by thermal oxidation. Both trigonal and tetragonal GeO2 exhibit excitation-dependent luminescence. Trigonal GeO2 exhibits strong green luminescence while tetragonal GeO2 exhibits strong blue luminescence when excited with ultra-violet light. Yellow-red luminescence is observed when both the phases are excited with green light. The emission wavelength varies almost linearly with the excitation wavelength both for trigonal and tetragonal GeO2. The variation is significant in the case of tetragonal GeO2, indicating a potential wavelength converter material.

The Relationship of Solid-State Plasticity to Mechanochromic Luminescence in Difluoroboron Avobenzone Polymorphs

In solid-state mechanochromic luminescence (ML) materials, it remains a challenge to establish the origin of fluorescence color changes upon mechanical action and to determine why only some fluorophores exhibit ML behavior. The study of mechanical properties by nanoindentation, followed by ML experiments on green- and cyan-emitting polymorphs of difluoroboron avobenzone reveals that upon smearing, the plastically deformable cyan form shows a prominent color change to yellow, while in the harder green form the redshifted emission is barely detectable. Crystal structure analysis reveals the presence of slip planes in the softer cyan form that can facilitate the formation of recoverable and low energy defects in the structure. Hence, the cyan form exhibits prominent and reversible ML behavior. This suggests a potential design strategy for efficient ML materials.

Room temperature synthesis of Mn2+ doped ZnS d-dots and observation of tunable dual emission: Effects of doping concentration, temperature, and ultraviolet light illumination

Mn2+ doped (0-50.0 molar %) ZnS d-dots have been synthesized in water medium by using an environment friendly low cost chemical technique. Tunable dual emission in UV and yellow-orange regions is achieved by tailoring the Mn2+ doping concentration in the host ZnS nanocrystal. The optimum doping concentration for achieving efficient photoluminescence (PL) emission is determined to be similar to 1.10 (at. %) corresponding to 40.0 (molar %) of Mn2+ doping concentration used during synthesis. The mechanism of charge transfer from the host to the dopant leading to the intensity modulated tunable (594-610 nm) yellow-orange PL emission is straightforwardly understood as no capping agent is used. The temperature dependent PL emission measurements are carried out, viz., in 1.10 at. % Mn2+ doped sample and the experimental results are explained by using a theoretical PL emission model. It is found that the ratio of non-radiative to radiative recombination rates is temperature dependent and this phenomenon has not been reported, so far, in Mn2+ doped ZnS system. The colour tuning of the emitted light from the samples are evident from the calculated chromaticity coordinates. UV light irradiation for 150 min in 40.0 (molar %) Mn2+ doped sample shows an enhancement of 33% in PL emission intensity. (C) 2013 American Institute of Physics. http://dx.doi.org/10.1063/1.4795779]

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.

Low temperature and rapid deposition of ZnO nanorods on Si(100) substrate with tunable optical emissions

This research article describes the large scale fabrication of ZnO nanorods of various shapes on Si(100) substrate, by using metalorganic precursor of Zn in solutions with microwave as the source of energy. This is a low temperature, environmental friendly and rapid thin film deposition process, where ZnO nanorods (1-3 mu m length) were grown only in 1-5 min of microwave irradiation. All as-synthesized nanorods are of single crystalline grown along the < 0001 > crystallographic direction. The coated nanorods were found to be highly dense having a thickness of similar to 1-3 mu m over the entire area 20 mm x 20 mm of the substrate. The ZnO thin film comprising of nanorods exhibits good adhesion with the substrate. A possible mechanism for the initial nucleation and growth of ZnO is discussed. A cross over from a strong visible light emission to an enhanced UV emission is observed, when the nature of the surfactants are varied from polymeric to ionic and nonionic. The position of the chromaticity coordinates in yellow region of the color space gives an impression of white light generation from these coatings by exciting with a blue laser.

Defect induced optical bandgap narrowing in undoped SnO2 nanocrystals

Unusual optical bandgap narrowing is observed in undoped SnO2 nanoparticles synthesized by the solution combustion method. The estimated crystallite size is nearly 7 nm. Though the quantum confinement effect predicts a larger optical bandgap for materials with small crystallite size than the bulk, the optical bandgap in the as synthesized materials is found to be 2.9 eV compared to the reported value of 3.6 eV for bulk SnO2 particles. The yellow-green photoluminescence emissions and the observed narrowing of the bandgap can be attributed to the deep donor levels of oxygen vacancies, owing to the high exothermicity of the combustion reaction and the faster cooling rates involved in the process.

Contrast in luminescence characteristics (intense UV to bright visible light) of ZnO nanostructures with the variation in microstructure

We report the controlled variation of luminescence of ZnO nanostructures from intense ultraviolet to bright visible light. Deliberate addition of surfactants in the reaction medium not only leads to growth anisotropy of ZnO, but also alters the luminescence property. ZnO nanoclusters comprising of very fine particles with crystallite sizes approximate to 15-22nm were prepared in a non-aqueous medium, either from a single alcohol or from their mixtures. Introduction of the aqueous solution of the surfactant helps in altering the microstructure of ZnO nanostructure to nanorods, nanodumb-bells as well as the luminescence property. The as-prepared powder material is found to be well crystallized. Defects introduced by the surfactant in aqueous medium play an important role in substantial transition in the optical luminescence. Chromaticity coordinates were found to lie in the yellow region of color space. This gives an impression of white light emission from ZnO nanocrystals, when excited by a blue laser. Oxygen vacancy is described as the major defect responsible for visible light emission as quantified by X-ray photoelectron spectroscopy and Raman analysis.

An Efficient Probe for Rapid Detection of Cyanide in Water at Parts per Billion Levels and Naked-Eye Detection of Endogenous Cyanide

A new molecular probe based on an oxidized bis-indolyl skeleton has been developed for rapid and sensitive visual detection of cyanide ions in water and also for the detection of endogenously bound cyanide. The probe allows the naked-eye detection of cyanide ions in water with a visual color change from red to yellow ((max)=80nm) with the immediate addition of the probe. It shows high selectivity towards the cyanide ion without any interference from other anions. The detection of cyanide by the probe is ratiometric, thus making the detection quantitative. A Michael-type addition reaction of the probe with the cyanide ion takes place during this chemodosimetric process. In water, the detection limit was found to be at the parts per million level, which improved drastically when a neutral micellar medium was employed, and it showed a parts-per-billion-level detection, which is even 25-fold lower than the permitted limits of cyanide in water. The probe could also efficiently detect the endogenously bound cyanide in cassava (a staple food) with a clear visual color change without requiring any sample pretreatment and/or any special reaction conditions such as pH or temperature. Thus the probe could serve as a practical naked-eye probe for in-field experiments without requiring any sophisticated instruments.

Rainbow Emission from an Atomic Transition in Doped Quantum Dots

Although semiconductor quantum dots are promising materials for displays and lighting due to their tunable emissions, these materials also suffer from the serious disadvantage of self-absorption of emitted light. The reabsorption of emitted light is a serious loss mechanism in practical situations because most phosphors exhibit subunity quantum yields. Manganese-based phosphors that also exhibit high stability and quantum efficiency do not suffer from this problem but in turn lack emission tunability, seriously affecting their practical utility. Here, we present a class of manganese-doped quantum dot materials, where strain is used to tune the wavelength of the dopant emission, extending the otherwise limited emission tunability over the yellow-orange range for manganese ions to almost the entire visible spectrum covering all colors from blue to red. These new materials thus combine the advantages of both quantum dots and conventional doped phosphors, thereby opening new possibilities for a wide range of applications in the future.

Stepwise Crystallization: Illustrative Examples of the Use of Metalloligands Cu-6(mna)(6)](6-) and (Ag-6(Hmna)(2)(mna)(4)](4-) (H(2)mna=2-Mercapto Nicotinic Acid) in the Formation of Heterometallic Two- and Three-Dimensional Assemblies with brucite, pcu, and sql Topologies

Three new inorganic coordination polymers, {Mn(H2O)(6)]-Mn-2(H2O)(6)](Cu-6(mna)(6)]center dot 6H(2)O}, 1, {Mn-4(OH)(2)(H2O)(10)] (Cu-6(mna)6]center dot 8H(2)O}, 2, and {Mn-2(H2O)(5)]Ag-6(Hmna)(2)(mna)(4)]center dot 20H(2)O}, 3, have been synthesized at room temperature through a sequential crystallization route. In addition, we have also prepared and characterized the molecular precursor Cu-6(Hmna)(6)]. Compounds 1 and 3 have a two-dimensional structure, whereas 2 has a three-dimensional structure. The formation of 2 has been achieved by minor modification in the synthetic composition, suggesting the subtle relationship between the reactant composition and the structure. The hexanudear copper and silver duster cores have Cu center dot center dot center dot Cu and Ag center dot center dot center dot Ag distances close to the sum of the van der Waals radii of Cu1+ and Ag1+, respectively. The connectivity between Cu-6(mna)(6)](6-) cluster units and Mn2+ ions gives rise to a brucite related layer in 1 and a pcu-net in 2. The Ag-6(Hmna)(2)(mna)(4)](4-) cluster in 3, on the other hand, forms a sql-net with Mn2+. Compound 1 exhibits an interesting and reversible hydrochromic behavior, changing from pale yellow to red, on heating at 70 degrees C or treatment under a vacuum. Electron paramagnetic resonance studies indicate no change in the valence states, suggesting the color change could be due to changes in the coordination environment only. The magnetic studies indicate weak antiferromagnetic behavior. Proton conductivity studies indicate moderate proton migrations in 1 and 3. The present study dearly establishes sequential crystallization as an important pathway for the synthesis of heterometallic coordination polymers.

Synthesis and photoluminescence properties of a novel Sr2CeO4:Dy3+ nanophosphor with enhanced brightness by Li+ co-doping

A series of Dy3+ (0.5-9 mol%) and Li+ (0.5-3 mol%) co-doped strontium cerate (Sr2CeO4) nanopowders are synthesized by low temperature solution combustion synthesis. The effects of Li+ doping on the crystal structure, chemical composition, surface morphology and photoluminescence properties are investigated. The X-ray diffraction results confirm that all the samples calcined at 900 degrees C show the pure orthorhombic (Pbam) phase. Scanning electron microscopy analysis reveals that the particles adopt irregular morphology and the porous nature of the product. Room temperature photoluminescence results indicate that the phosphor can be effectively excited by near UV radiation (290 to 390 nm) which results in the blue (484 nm) and yellow (575 nm) emission. Furthermore, PL emission intensity and wavelength are highly dependent on the concentration of Li+ doping. The emission intensity is enhanced by similar to 3 fold with Li+ doping. White light is achieved by merely varying dopant concentration. The colour purity of the phosphor is confirmed by CIE co-ordinates (x = 0.298, y = 0.360). The study demonstrates a simple and efficient method for the synthesis of novel nanophosphors with enhanced white emission.

Exclusive Detection of Sub-Nanomolar Levels of Palladium(II) in Water: An Excellent Probe for Multiple Applications

A new colorimetric probe has been developed for the detection and estimation of Pd-II at sub-nanomolar concentrations. The probe consisted of rhodamine (signaling unit), which was linked with a bis-picolyl moiety (binding site) through a phenyl ring. Pd-II induced opening of the spirolactam ring of the probe with the generation of a prominent pink color. The excellent selectivity of the probe towards Pd-II over Pd-0 or Rh-II ensured its potential utility for the detection of residual palladium contamination in pharma-ceutical drugs and in Pd-catalyzed reactions. The probe showed a ``turn-on'' (bright yellow) fluorescence upon the addition of Pd-II, which made it suitable for the detection of Pd contaminants in mammalian cells.

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.

Defect induced optical bandgap narrowing in undoped SnO2 nanocrystals

Unusual optical bandgap narrowing is observed in undoped SnO2 nanoparticles synthesized by the solution combustion method. The estimated crystallite size is nearly 7 nm. Though the quantum confinement effect predicts a larger optical bandgap for materials with small crystallite size than the bulk, the optical bandgap in the as synthesized materials is found to be 2.9 eV compared to the reported value of 3.6 eV for bulk SnO2 particles. The yellow-green photoluminescence emissions and the observed narrowing of the bandgap can be attributed to the deep donor levels of oxygen vacancies, owing to the high exothermicity of the combustion reaction and the faster cooling rates involved in the process. (C) 2013 Author(s). All article content, except where otherwise noted, is licensed under a Creative Commons Attribution 3.0 Unported License.

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.