Fabrication of Europium-Doped CaF2 Films via Sol-Gel Synthesis as Down-Shifting Layers for Solar Cell Applications

In the present work, an in-depth study on the sol-gel process for the fabrication of Eu-doped CaF2 materials in the form of thin films has been addressed for the production of down-shifting layers. Fine-tuning of the operative parameters, such as the annealing temperature, substrate nature and doping ion percentage, has been finalized in order to obtain Eu(III)-doped CaF2 thin films via a reproducible and selective solution process for down-shifting applications. An accurate balance of such parameters allows for obtaining films with high uniformity in terms of both their structural and compositional features. The starting point of the synthesis is the use of a mixture of Ca(hfa)(2)center dot diglyme center dot H2O and Eu(hfa)(3)center dot diglyme adducts, with a suited ratio to produce 5%, 10% and 15% Eu-doped CaF2 films, in a water/ethanol solution. A full investigation of the structural, morphological and compositional features of the films, inspected using X-ray diffraction analysis (XRD), field emission scanning electron microscopy (FE-SEM) and energy dispersive X-ray analysis (EDX), respectively, has stated a correlation between the annealing temperature and the structural characteristics and morphology of the CaF2 thin films. Interestingly, crystalline CaF2 films are obtained at quite low temperatures of 350-400 degrees C. The down-shifting properties, validated by taking luminescence measurements under UV excitation, have allowed us to correlate the local environment in terms of the degree of symmetry around the europium ions with the relative doping ion percentages

Strukturna i dielektrična svojstva nanostrukturnih prahova BaTiO3 punjenih ionima Eu3+ I pripremljenih sol-gel procesom

Nano-structure BaTiO3 powders doped with Eu3+ ions have been prepared by a sol-gel technique. X-ray diffraction (XRD) results indicate that BaTiO3 gel powders crystallize into tetragonal symmetry on heat treatment at 750 ◦C. Particle sizes as small as 3.5 nm were measured for pure BaTiO3 powders. The XRD data were confirmed by transmission electron microscope. Room-temperature luminescence spectra of BaTiO3:0.5% Eu3+, BaTiO3:1% Eu3+ and BaTiO3:2% Eu3+ powders have been measured. The luminescence spectra of prepared ultrafine powders are dominated by the 5D0 →7F2 transition in Eu3+, suggesting a strong distortion of the Eu3+ sites. The foreign ions are mainly accommodated in Ba2+ tetragonal sites, which are then distorted by the occurrence of different ionic charge of the two cations Ba2+ and Eu3+. The dielectric constant, ε, of BaTiO3, BaTiO3:0.5% Eu3+, BaTiO3:1% Eu3+ and BaTiO3:2% Eu3+ powders at frequency 100 Hz was found to be equal to 1000, 1211, 1455 and 1800, respectively. This high dielectric constant is believed to arise from the increase of the crystallite size, when increasing the concentration of Eu3+ ions. After annealing in argon at 400 ◦C for two hours, at 100 Hz, the dielectric constant of the pure sample was 625 and the AC resistivity also decreased. The room temperature (RT) AC resistivity of the samples depends on the concentration of Eu3+ ions in BaTiO3 powders, and was found to decrease as the concentration of Eu3+ ions increased.Pripremali smo sol-gel metodom nanostrukturne prahove BaTiO3 punjene Eu3+ ionima. Difrakcija X-zračenja (DXZ) pokazuje da se gel prahovi BaTiO3 kristaliziraju u tetragonalnoj simetriji zagrijavanjem na 750 ◦C. Utvrdili smo veličine zrna od samo 3.5 nm u čistom prahu BaTiO3. Podatke od DXZ potvrdili smo prolaznom elektronskom mikroskopijom. Mjerili smo fotoluminescentne spektre prahova BaTiO3:0.5% Eu3+, BaTiO3:1% Eu3+ i BaTiO3:2% Eu3+ na sobnoj temperaturi. U luminescentnim spektrima pripremljenih ultrafinih prahova prevladava prijelaz 5D0 →7F2 u Eu3+, što ukazuje na snažna izobličenja na mjestima Eu3+ iona. Ugrađeni se ioni Eu3+ uglavnom smještaju na tetragonalne položaje Ba2+, a velika razlika ionskih naboja dvaju kationa, Ba2+ i Eu3+, uzrokuje snažne promjene oko tog defekta. Dielektrične konstante, ε, prahova BaTiO3, BaTiO3:0.5% Eu3+, BaTiO3:1% Eu3+ i BaTiO3:2% Eu3+ na frekvenciji 100 Hz prema našim mjerenjima iznose 1000, 1211, 1455 odn. 1800. Smatramo da su tako velike vrijednosti dielektrične konstante posljedica povećanih veličina kristalita za veća punjenja ionima Eu3+. Nakon opuštanja u argonu na 400 ◦C tijekom dva sata, dielektrična konstanta čistog praha bila je 625, a otpornost se također smanjila. Izmjenična otpornost prahova BaTiO3 ovisi o punjenju ionima Eu3+ i nalazi se da se smanjuje kada se poveća sadržaj iona Eu3+

Chirality in luminescent Cs3Cu2Br5 microcrystals produced via ligand-assisted reprecipitation

Herein we report new chiral luminescent Cs3Cu2Br5 needle-like microcrystals and the analysis of their optical properties and the effect of the ligand structure on the transfer of chirality

Unraveling the impact of different thermal quenching routes on the luminescence efficiency of the Y3Al5O12:Ce3+ phosphor for white light emitting diodes

Cerium doped yttrium aluminium garnet, Y3-zCezAl5O12, is the prototype material for solid-state white lighting and it still is an important white LED phosphor. However, fundamental understanding of the thermal quenching of luminescence, which leads to a pronounced reduction of the emission intensity under high-power light-emitting diode operation, remains to be obtained. Here we show, through a multitechnique approach based on photoluminescence, thermoluminescence and mode-selective vibrational excitation experiments that thermal quenching of luminescence in Y3-zCezAl5O12 is caused by a combined effect of thermal ionization, thermally activated concentration quenching, and thermally activated 5d → 4f crossover relaxation via electron-phonon coupling, and establish the general trends upon variation of the Ce3+ concentration and temperature. Thermal quenching below 600 K is primarily the result of concentration quenching and crossover relaxation, which can be suppressed by keeping the Ce3+ dopant concentration far below 0.7 mol%, whereas for temperatures above 600 K thermal ionization is the predominating quenching process. This new insight into the interplay between different thermal quenching processes provides design principles for optimizing the light emittance and colour stability of new phosphor materials used in white lighting devices characterized by certain operating temperatures. This journal i

Physical–chemical properties of biogenic selenium nanostructures produced by Stenotrophomonas maltophilia SeITE02 and Ochrobactrum sp. MPV1

Stenotrophomonas maltophilia SeITE02 and Ochrobactrum sp. MPV1 were isolated from the rhizosphere soil of the selenium-hyperaccumulator legume Astragalus bisulcatus and waste material from a dumping site for roasted pyrites, respectively. Here, these bacterial strains were studied as cell factories to generate selenium-nanostructures (SeNS) under metabolically controlled growth conditions. Thus, a defined medium (DM) containing either glucose or pyruvate as carbon and energy source along with selenite (www.frontiersin.org) was tested to evaluate bacterial growth, oxyanion bioconversion and changes occurring in SeNS features with respect to those generated by these strains grown on rich media. Transmission electron microscopy (TEM) images show extra- or intra-cellular emergence of SeNS in SeITE02 or MPV1 respectively, revealing the presence of two distinct biological routes of SeNS biogenesis. Indeed, the stress exerted by www.frontiersin.org upon SeITE02 cells triggered the production of membrane vesicles (MVs), which surrounded Se-nanoparticles (SeNPsSeITE02-G_e and SeNPsSeITE02-P_e with average diameter of 179 ± 56 and 208 ± 60 nm, respectively), as highlighted by TEM and scanning electron microscopy (SEM), strongly suggesting that MVs might play a crucial role in the excreting mechanism of the SeNPs in the extracellular environment. On the other hand, MPV1 strain biosynthesized intracellular inclusions likely containing hydrophobic storage compounds and SeNPs (123 ± 32 nm) under pyruvate conditioning, while the growth on glucose as the only source of carbon and energy led to the production of a mixed population of intracellular SeNPs (118 ± 36 nm) and nanorods (SeNRs; average length of 324 ± 89). SEM, fluorescence spectroscopy, and confocal laser scanning microscopy (CLSM) revealed that the biogenic SeNS were enclosed in an organic material containing proteins and amphiphilic molecules, possibly responsible for the high thermodynamic stability of these nanomaterials. Finally, the biogenic SeNS extracts were photoluminescent upon excitation ranging from 380 to 530 nm, whose degree of fluorescence emission (λem = 416–640 nm) was comparable to that from chemically synthesized SeNPs with L-cysteine (L-cys SeNPs). This study offers novel insights into the formation, localization, and release of biogenic SeNS generated by two different Gram-negative bacterial strains under aerobic and metabolically controlled growth conditions. The work strengthens the possibility of using these bacterial isolates as eco-friendly biocatalysts to produce high quality SeNS targeted to possible biomedical applications and other biotechnological purposes

Morphology and luminescence of nanocrystalline Nb₂O₅ doped with Eu³⁺

The synthesis of nanocrystalline Nb2O5:Eu3+ has been achieved by using a Pechini procedure. The obtained materials are single-phase niobia with the orthorhombic structure, average crystallite size around 25nm and average lattice strain of about 0.002. TEM images show that the particles are rectangular and reasonably isolated. The luminescence of the Eu3+ ions in the niobia lattice is efficient and affected by a strong inhomogeneous broadening, due to an important disorder around the lanthanide ions

Growth and microstructural analysis of nanosized Y2O3 doped with rare-earths

Nanosized cubic Y2O3 samples, undoped and doped with 10 mol% Nd2O3, Eu2O3, Gd2O3, Tb2O3, Ho2O3 and Er2O3 (Y(1.8)Ln(0.2)O(3), where Ln=Nd, Eu, Gd, Tb, Ho or Er), were prepared by means of a controlled hydrolysis method in an aqueous solution containing ammonia, Y(NO3)(3) and Ln(NO3)(3) as precursors, and a surface modifier. The microstrain and the average size of the diffraction domains have been calculated from the XRD patterns and the results have been compared with those obtained by a combustion synthesis. It is shown that the cell parameter of the C-M2O3 (bcc structure related to the CaF2 structure; the M atom is 6-coordinated) structure of doped Y2O3 is correlated to the ion size of the dopant. The shape of the crystallites appears to be needle-like in all cases, while the microstrains depend on the dopant and are probably due to surface effect. XRD and Raman analysis show that, despite the heavy doping, only one phase in the Y2O3 powders is present. (C) 2000 Elsevier Science S.A. All rights reserved

Temperature dependence and temporal dynamics of Mn2+ upconversion luminescence sensitized by Yb3+ in codoped LaMgAl11O19

A detailed spectroscopic study of the upconversion properties in Mn2+-Yb3+ codoped LaMgAl11O19 is presented. Pulsed and continuous-wave infrared excitation in the 2F7/2--2F5/2 Yb3+ absorption peaks induces broad Mn2+ green emission at 19450 cm-1, which is assigned to the 4T1--6A1 transition in tetrahedral Mn2+ and sharp peaks associated with Yb3+-pairs luminescence. Both emissions have very different temporal evolution and can be separated by time-resolved spectroscopy. Among the different concentrations under investigation, the 2%Mn2+-5%Yb3+ codoped system presents the highest upconversion efficiency. The corresponding emission remains visible to the naked eye up to 650 K. The time dependence of the Mn2+ luminescence upon Yb3+ excitation shows distinct behaviors for different doping concentrations. The temporal evolution of the intensity for the diluted system doped with 2%Mn2+ and 5%Yb3+ together with the pure manganese compound doped with 1%Yb3+, as well as the temperature dependence of the upconversion emission intensity and lifetime are relevant to identify the underlying upconversion mechanisms. We show that the main processes responsible for upconversion in this doubly transition-metal rare-earth doped oxide are both ground-state absorption (GSA)/excited-state absorption and GSA/energy-transfer upconversion. An analysis of these processes yielding highly efficient luminescence is discussed on the basis of crystal structure and dopants.This work was financially supported by the Spanish Ministerio de Ciencia e Innovación (Project No. MAT2008- 06873-C02-01/MAT) and the MALTA-Consolider Ingenio 2010 (Reference No. CSD2007-00045). R.M.-R. thanks the Spanish MEC for a FPI research grant (Reference No. BES-2006-13359)

Assessing Single Upconverting Nanoparticle Luminescence by Optical Tweezers

We report on stable, long-term immobilization and localization of a single colloidal Er3+/Yb3+ codoped upconverting fluorescent nanoparticle (UCNP) by optical trapping with a single infrared laser beam. Contrary to expectations, the single UCNP emission differs from that generated by an assembly of UCNPs. The experimental data reveal that the differences can be explained in terms of modulations caused by radiation-trapping, a phenomenon not considered before but that this work reveals to be of great relevanceThis work was supported by the Spanish Ministerio de Educación y Ciencia (MAT2010–16161 and MAT2013–47395-C4–1-R). P.H.G. thanks the Spanish Ministerio de Economía y Competitividad (MINECO) for the Juan de la Cierva program. P.R.S thanks the Spanish Ministerio de Economía y Competitividad (MINECO) for the “Promoción 14 del talento y su Empleabilidad en I+D+i” statal program. Fondazione Cariverona (Verona, Italy) is gratefully acknowledged for financial support in the frame of the project “Verona Nanomedicine Initiative