A triazolium-based fluorophore intercalated in layered double hydroxides: from simple syntheses to bright solid-state luminescence.

This study presents the intercalation into Layered Double Hydroxides (LDHs) of two sulfonated organic molecules featuring the mesoionic triazolium scaffold. These sulfonated fluorophores exhibited excellent solubility in aqueous basic solutions, facilitating their compatibility with the synthesis of LDHs through coprecipitation methods. We applied the size-matching interlayer space (SMIS) approach by substituting a portion of a mono- or dianionic surfactant used in LDH preparation by the sulfonated fluorophore, we aimed to match the size of the luminescent interleaved guest effectively. Our investigation focused on two anion spacers: the classic monoanionic dodecyl sulfate (DS) and the dianionic phenylene dipropionate (PPA). Our results indicated that the latter spacer allowed a more efficient insertion of the fluorescent guest. Thermal resistance analysis underscored the robustness of the final hybrid materials, suggesting a promising design strategy for luminescent materials when applied in diverse applications.

Polymeric copper(I)-NHC complexes with bulky bidentate (N

Starting from imidazolium chlorides bearing bulky nitrogen donors, a series of four complexes, mainly [Cu(C^N)Cl]n coordination polymers were obtained directly as luminescent species by simple filtration from the aqueous reaction medium, highlighting a simple, eco-friendly, robust and reproducible synthetic procedure. Additionally, we have shown on the most efficient example that chloride could be exchanged very easily by other halides/pseudohalides (Br-, I-, NCS-, N3-) allowing to slightly modulate the emitted colour while conserving the polymeric structure, except for azide for which a dimer was obtained. The combination of chemical analyses, of photoluminescence studies in the solid state including quantum yield measurement and X-ray diffraction on single crystals and as-synthesized microcrystalline powders highlighted that the polymeric luminescent species was indeed obtained directly by simple filtration and that no major alteration of the structure was observed upon recrystallisation. Samples of all polymeric complexes displayed remarkable stability towards air oxidation remaining unchanged upon storage for several months and partially retaining their photoluminescence properties even after a thermal treatment at 100 °C for 24 h.

Nanostructuration of YAG:Ce Coatings by ZnO Nanowires: A Smart Way to Enhance Light Extraction Efficiency.

In this study, we report on the enhancement of the light extraction efficiency of sol-gel-derived Y3Al5O12:Ce3+ (YAG:Ce) coatings using ZnO nanowire (NW) arrays. The ZnO NWs were grown by hydrothermal synthesis from a ZnO seed layer directly deposited on a YAG:Ce coating. Highly dense and vertically aligned ZnO NW arrays were evidenced on the top of the YAG:Ce coating by electron microscopy. A photoluminescence study showed that this original design leads to a different angular distribution of light together with an increase in emission efficiency of the YAG:Ce coating upon blue excitation, up to 60% more efficient compared to a non-structured YAG:Ce coating (without NWs). These improvements are ascribed to multi-scattering events for photons within the structure, allowing them to escape from the phosphor layer by taking optical paths different from those of the non-structured coating. This strategy of light extraction enhancement appears to be very promising, since it uses soft chemical processes and cheap ZnO NWs and is applicable to any sol-gel-derived luminescent coating.

A First Wide-Open LDH Structure Hosting InP/ZnS QDs: A New Route Toward Efficient and Photostable Red-Emitting Phosphor.

The architecture of Zn-Al layered double hydroxides (LDHs), organo-modified with bola-amphiphiles molecules, is matching its interlayer space to the size of narrow-band red-emitting InP/ZnS core-shell quantum dots (QDs) to form original high-performance functional organic-inorganic QD-bola-LDH hybrids. The success of size-matching interlayer space (SMIS) approach is confirmed by X-ray diffraction, small angle X-ray scattering (SAXS), TEM, STEM-HAADF, and photoluminescence investigations. The QD-Bola-LDH hybrid exhibits a photoluminescence quantum yield three times higher than that of pristine InP/ZnS QDs and provides an easy dispersion into silicone-based resins, what makes the SMIS approach a change of paradigm compared to intercalation chemistry using common host structures. Moreover, this novel hybrid presents low QD-QD energy transfer comparable to that obtained for QDs in suspension. Composite silicone films incorporating InP/ZnS (0.27 wt%) QD-bola-LDH hybrids further show remarkable improved photostability relative to pristine QDs. An LED overlay consisting of a blue LED chip and silicone films loaded with QD-bola-LDH hybrids and YAG:Ce phosphors exhibits a color rendering index close to 94.

Investigation of the Incorporation of Cerium Ions in MCVD-Silica Glass Preforms for Remote Optical Fiber Radiation Dosimetry.

The incorporation of Ce3+ ions in silicate glasses is a crucial issue for luminescence-based sensing applications. In this article, we report on silica glass preforms doped with cerium ions fabricated by modified chemical vapor deposition (MCVD) under different atmospheres in order to favor the Ce3+ oxidation state. Structural analysis and photophysical investigations are performed on the obtained glass rods. The preform fabricated under reducing atmosphere presents the highest photoluminescence (PL) quantum yield (QY). This preform drawn into a 125 µm-optical fiber, with a Ce-doped core diameter of about 40 µm, is characterized to confirm the presence of Ce3+ ions inside this optical fiber core. The fiber is then tested in an all-fibered X-ray dosimeter configuration. We demonstrate that this fiber allows the remote monitoring of the X-ray dose rate (flux) through a radioluminescence (RL) signal generated around 460 nm. The response dependence of RL versus dose rate exhibits a linear behavior over five decades, at least from 330 µGy(SiO2)/s up to 22.6 Gy(SiO2)/s. These results attest the potentialities of the MCVD-made Ce-doped material, obtained under reducing atmosphere, for real-time remote ionizing radiation dosimetry.

Towards rare-earth-free white light-emitting diode devices based on the combination of dicyanomethylene and pyranine as organic dyes supported on zinc single-layered hydroxide.

A new luminescent composite film resulting from the dispersion of luminescent organic dyes in a single-layered hydroxide (SLH)-type inorganic matrix has been developed. Two fluorescent organic dyes emitting visible light upon blue LED excitation were investigated in this study: dicyanomethylene (DCM) and pyranine (HPTS). These dyes exhibit broad emission bands that cover a large part of the visible spectrum. The concept developed in our work consisted in keeping SLH in its wet form to ensure a good dispersion of the fluorescent dyes prior to immobilizing the hybrid materials in a silicone polymer to achieve luminescent composite films. We demonstrate that these coatings stacked upon each other and placed above a blue LED lead to white-light emission with suitable photometric parameters for applications in lighting or display devices: colour temperature of 5409 K and colour rendering index (CRI) of 81.

Coupling Photoluminescence and Ionic Conduction Properties Using the Different Coordination Sites of Ureasil-Polyether Hybrid Materials.

In this article, we demonstrate that each functional group of ureasil organic-inorganic hybrid (OIH) materials can act as a specific coordination site for a given active guest species, hence allowing the possibility of combining different functional properties. To illustrate this concept, the sol-gel process was used to produce diurea cross-linked siloxane-polyethylene oxide (U-PEO) and siloxane-polypropylene oxide (U-PPO) hybrid host frameworks with similar molecular weights (1900 and 2000 g mol-1 for PEO and PPO, respectively), with Li+ and Eu3+ as active guest ions providing ionic conduction and photoluminescence (PL) properties, respectively. Comparison of Fourier transform infrared spectra and small-angle X-ray scattering results for single-doped (using Li+ or Eu3+) and co-doped (using Li+ and Eu3+) U-PEO and U-PPO hosts showed that in every case, there was specific coordination of Eu3+ by the carbonyl group of the urea bridge and of Li+ by ether-type oxygen of the PEO and PPO chains. Optical analyses demonstrated that loading with Li+ did not affect the luminescence properties of the Eu3+-loaded OIH. Although loading with Eu3+ had a small effect on ionic transport, co-doping with Li+ ions ensured macroscopic ion-conduction of the transparent and luminescent hybrid material. The results suggested that the combination of both properties in a transparent elastomeric material could be useful for the development of multifunctional devices. The results suggested that the combination of both properties in a transparent elastomeric material could be useful for the development of multifunctional polyelectrolytes applied in the field of dual luminescent devices such as photoelectrochromic smart windows.

Investigation on combustion derived BaMgAl10O17:Eu2+ phosphor powder and its corresponding PVP/BaMgAl10O17:Eu2+ nanocomposite.

This work focuses on the study of BaMgAl10O17:Eu(2+) (BAM:Eu) nanophosphors prepared by a microwave-assisted combustion procedure and more especially on the polymer/BAM:Eu nanocomposite film suitable for optical devices such as solid-state-lighting. Powder presented a specific nanomorphology, highly friable and thus easily ground into fine particles. They were then homogeneously dispersed into a polymer solution (poly(N-vinylpyrrolidone) or PVP) to elaborate a polymer phosphor nanocomposite. The structural, morphological and optical features of the nanocomposite film have been studied and compared to those of a pristine PVP film and BAM:Eu powder. All the characterizations (XRD, SEM, SAXS, etc.) proved that the blue phosphor nanoparticles are well incorporated into the polymer nanocomposite film which exhibited the characteristic blue emission of Eu(2+) under UV light excitation. Furthermore, the photostability of the polymer/phosphor nanocomposite film has been studied after exposure to accelerated artificial photoageing at wavelengths above 300 nm.

Ce-doped YAG nanophosphor and red emitting CuInS2/ZnS core/shell quantum dots for warm white light-emitting diode with high color rendering index.

In this work, we report the solvothermal synthesis of Ce-doped YAG (YAG:Ce) nanoparticles (NPs) and their association with a free-Cd CuInS2/ZnS (CIS/ZnS) core/shell QDs for application into white light emitting diode (WLED). 1500 °C-annealed YAG:Ce NPs and CIS/ZnS core/shell QDs exhibited intense yellow and red emissions band with maxima at 545 and 667 nm, respectively. Both YAG:Ce nanophosphor and CIS/ZnS QDs showed high photoluminescence quantum yield (PL QY) of about 50% upon 460 nm excitation. YAG:Ce nanophosphor layer and bilayered YAG:Ce nanophosphor-CIS/ZnS QDs were applied on blue InGaN chip as converter wavelength to achieve WLED. While YAG:Ce nanophosphor converter layer showed low color rendering index (CRI) and cold white light, bilayered YAG:Ce nanophosphor-CIS/ZnS QDs displayed higher CRI of about 84 and warm white light with a correlated color temperature (CCT) of 2784 K. WLED characteristics were measured as a function of forward current from 20 to 1200 mA. The white light stability of bilayered nanophosphor-QDs-based WLED operated at 200 mA was also studied as a function of operating time up to 40 h. Interestingly, CRI and CCT of such device tend to remain constant after 7 h of operating time suggesting that layer-by-layer structure of YAG:Ce phosphor and red-emitting CIS/ZnS QDs could be a good solution to achieve stable warm WLED, especially when high current density is applied.

Comparative study of physico-mechanical and antioxidant properties of edible gelatin films from the skin of cuttlefish.

Physicochemical properties of edible films based on cuttlefish skin gelatin extracted without (G0) or with different concentrations of pepsins (5 (G5), 10 (G10) and 15 (G15) U/g of skin) were investigated. Edible films prepared with partially hydrolyzed gelatins had lower tensile strength (TS) and elongation at break (EAB), but higher water vapour permeability (WVP) and water solubility than the control film. FTIR spectra of obtained gelatin films revealed a significant loss of molecular order of the triple helix. In addition, differential scanning calorimetric (DSC) analysis indicated that partially hydrolyzed gelatine films exhibited lower transition temperature and enthalpy compared with those of control film. The properties of the films were related to their microstructure, which was observed by scanning electron microscopy. Films with G0 and G5 had a smooth surface and a more compact structure, while films prepared with G10 and G15 had coarser surface. Thus, the chain length of extracted gelatin directly affected the properties of corresponding films.

Luminescent nanocomposites made of finely dispersed Y3Ga5O12:Tb powder in a polymer matrix: promising candidates for optical devices.

This paper reports the initial results of an original and simple method to elaborate flexible, self-standing, and thick luminescent films suitable for optical devices. PVP/Y(3)Ga(5)O(12):Tb(3+) nanocomposite films have been successfully achieved from a sol-gel derived Y(3)Ga(5)O(12):Tb(3+) powder and an alcoholic solution of poly-N-vinylpyrrolidone (PVP). The structural, morphological, and optical properties of these nanocomposite films have been studied and compared to those of a pristine PVP film and Y(3)Ga(5)O(12):Tb(3+) powder. The nanocomposite films were characterized by infrared and Raman spectroscopies as well as scanning and transmission electron microscopies (SEM and TEM) and demonstrated good dispersion of the phosphor particles within the polymer matrix via an alveolar mesostructure. The optical properties of these nanocomposites were fully characterized, and both their excitation and emission spectra and decay curves were recorded. Furthermore, photostability of the nanocomposite films and of the luminescent raw powder has been studied after exposure to an accelerated artificial photoageing at wavelengths higher than 300 nm. The elaboration process used is both tunable and applicable to a large variety of powders and polymers because it does not require any additive to form homogeneous and easily shapeable phosphor/polymer nanocomposites applicable in a large variety of optical devices such as solid-state-lighting.

Modifications involved by acetylacetone in properties of sol-gel derived Y(3)Al(5)O(12):Tb(3+)- II: optical features.

Tb(3+)-doped Y(3)Al(5)O(12) powders have been synthesized from alkoxide precursors using, or not using, acetylacetone as a chemical modifier. The terbium oxidation state and local environment of amorphous and crystallized powders have been comparatively investigated by means of X-ray absorption near-edge structures (XANES) and extended X-ray absorption fine structure (EXAFS) while laser-induced luminescence was used to study their optical properties. Excitation and emission spectra have been recorded and a relative luminescence yield has been assessed upon 277 nm excitation. Whatever the sample, the terbium oxidation state remains +III and, for a similar heating treatment until 900 degrees C, its local environment appears to be better organized in powders modified by acetylacetone. Structural parameters obtained during XAS study are consistent with the YAG structure in which Tb atoms are in solid solution with Y ones. Besides, Tb(3+) characteristic green luminescence has been recorded for all samples, even those amorphous. It has been evidenced that the use of acetylacetone leads to more efficient luminescent materials for calcination temperatures ranging from 400 degrees C to 900 degrees C upon 277 nm excitation. Discrepancies between optical properties will be discussed with regards to the terbium local environment and expected luminescence features.

Modifications induced by acetylacetone in properties of sol-gel derived Y(3)Al(5)O(12) : Tb(3+)- I: structural and morphological organizations.

Acetylacetone has been used as a chemical modifier for the synthesis of undoped and Tb(3+)-doped Y(3)Al(5)O(12) powders. A systematic investigation concerning its influence on the structural and morphological properties of amorphous and crystallized samples has been carried out. These properties have been comparatively studied by means of X-ray diffraction, infrared spectroscopy, SEM, XAS and SAXS. (27)Al NMR and EPR experiments have been performed to complete the study. The combined results have evidenced that acetylacetone promotes organic groups departure during calcination, entailing a better structural organization at lower temperatures compared with unmodified powders. Structuration has been proven to occur at short-scale range until a 600 degrees C heating treatment before being extended by coalescence at higher temperatures. Finally, the presence of acac ligands on the alkoxides leads to a monomer-cluster aggregation process, and thus to a more open network.

Eu-doped BaTiO3powder and film from sol-gel process with polyvinylpyrrolidone additive.

Transparent BaTiO(3):Eu(3+) films were prepared via a sol-gel method and dip-coating technique, using barium acetate, titanium butoxide, and polyvinylpyrrolidone (PVP) as modifier viscosity. BaTiO(3):Eu(3+) films ~500 nm thick, crystallized after thermal treatment at 700 masculineC. The powders revealed spherical and rod shape morphology. The optical quality of films showed a predominant band at 615 nm under 250 nm excitation. A preliminary luminescent test provided the properties of the Eu(3+) doped BaTiO(3).