Flexible translucent persistent luminescent films based on Sr2MgSi2O7:Eu2+,Dy3+ cellulose ether composites.

Persistent luminescent materials are present in several recent studies on new applications and novel properties. In this work, we demonstrate, for the first time, the production of translucent flexible persistent composites based on Sr2MgSi2O7:Eu2+,Dy3+ (SMSO) into cellulose ether matrix film. The composite was successfully prepared through a new optimized route of co-precipitation and microwave-assisted annealing followed by (3-aminopropyl)triethoxysilane (APTES) coating and dispersion in hydroxypropyl methylcellulose (HPMC). The SMSO@APTES/HPMC films show persistent luminescence emission at 475 nm (blue) and high transmittance in the visible range. To understand the fine distribution of the nanoparticles in the matrix, we have investigated their structure and dispersion by using Synchrotron Radiation X-ray fluorescence mapping and Scanning Transmission X-ray Microscopy. This innovative composite could bring new perspectives for the class of persistent luminescence materials, enhancing technologies in progress throwing light on new applications never perceived.

Spectroscopic study of the 4fn-15dtransitions of LaPO4doped with Pr3+ or co-doped with Pr3+ and Gd3+ in the vacuum ultra violet region.

The energy off-dtransitions depends on the crystalline field in which the lanthanide ion is inserted. Depending on the experimental setup, these transitions could occur at high energy, so several studies regarding theoretical data have been conducted. Here, we present the experimental determination of the energy of interconfigurational 4fn â†’ 4fn-15d (f-d)transitions from Pr3+ions to the lanthanum orthophosphate LaPO4matrix; we have also determined the bandgap value for this host. The experiments were carried out at the Synchrotron setup of the Brazilian LNLS laboratory. Specifically, we synthesized LaPO4:Pr3+and LaPO4:Pr3+/Gd3+by the hydrothermal method under different pH conditions or by spray pyrolysis. The particles resulting from hydrothermal synthesis had different morphologies and the influence of pH value was showed: the reaction medium was controlled along the process, which changed the surface potential. On the basis of Raman spectroscopy and x-ray diffraction analyses, we found that the crystalline phase was monoclinic monazite for all the samples. We studied the 4f5dlevel and bandgap transitions at high energy by absorption analysis in the VUV range. The experimental results were 7.5 eV (LaPO4bandgap) and 5 eV (4fn→ 4fn-15dtransition of the Pr3+ion), which were close to the theoretical values reported in the literature for this ion and this matrix.

Opportunities for Persistent Luminescent Nanoparticles in Luminescence Imaging of Biological Systems and Photodynamic Therapy.

The use of luminescence in biological systems allows us to diagnose diseases and understand cellular processes. Persistent luminescent materials have emerged as an attractive system for application in luminescence imaging of biological systems; the afterglow emission grants background-free luminescence imaging, there is no need for continuous excitation to avoid tissue and cell damage due to the continuous light exposure, and they also circumvent the depth penetration issue caused by excitation in the UV-Vis. This review aims to provide a background in luminescence imaging of biological systems, persistent luminescence, and synthetic methods for obtaining persistent luminescent materials, and discuss selected examples of recent literature on the applications of persistent luminescent materials in luminescence imaging of biological systems and photodynamic therapy. Finally, the challenges and future directions, pointing to the development of compounds capable of executing multiple functions and light in regions where tissues and cells have low absorption, will be discussed.

Structural and optical properties of europium- and titanium-doped Y2 O3 nanoparticles.

Luminescent nanoparticles of Y2 O3 doped with europium (Eu) and/or titanium (Ti) were synthesized using modified sol-gel routes. The crystalline cubic phase was confirmed using X-ray powder diffraction (XRD). Particle morphology and size were evaluated using scanning and transmission electron microscopy. High-resolution transmission electron microscopy showed that the synthesis method affected the average particle size and the Fourier transform of the images showed the lattice plane distances, indicating that the samples presented high crystallinity degree in accordance with the XRD pattern. The Ti valence was investigated using X-ray absorption near edge spectroscopy and the tetravalent form was the dominant oxidizing state in the samples, mainly in Eu and Ti co-doped Y2 O3 . Optical behaviour was investigated through X-ray excited optical luminescence and photoluminescence under ultraviolet-visible (UV-vis) and vacuum ultraviolet (VUV) excitation. Results indicated that Eu3+ is the emitting centre in samples doped with only Eu and with both Eu and Ti with the 5 D0 →7 F2 transition as the most intense, indicating Eu3+ in a noncentrosymmetric site. Finally, in the Eu,Ti-doped Y2 O3 system, Ti3+ (or TiIV ) excitation was observed but no Ti emission was present, indicating a very efficient energy transfer process from Ti to Eu3+ . These results can aid the development of efficient nanomaterials, activated using UV, VUV, or X-rays.

Red- and green-emitting nano-clay materials doped with Eu3+ and/or Tb3.

Trivalent europium (Eu3+ ) and terbium (Tb3+ ) ions are important activator centers used in different host lattices to produce red and green emitting materials. The current work shows the design of new clay minerals to act as host lattices for rare earth (RE) ions. Based on the hectorite structure, nano-chlorohectorites and nano-fluorohectorites were developed by replacing the OH- present in the hectorite structure with Cl- or F- , thus avoiding the luminescence quenching expected due to the OH- groups. The produced matrices were characterized through X-ray powder diffraction (XPD), transmission electron microscopy (TEM), FT-IR, 29 Si MAS (magic angle spinning) NMR, nitrogen sorption, thermogravimetry-differential scanning calorimetry (TGA-DSC) and luminescence measurements, indicating all good features expected from a host lattice for RE ions. The nano-clay materials were successfully doped with Eu3+ and/or Tb3+ to yield materials preserving the hectorite crystal structure and showing the related luminescence emissions. Thus, the present work shows that efficient RE3+ luminescence can be obtained from clays without the use of organic 'antenna' molecules.

Rapid and Energy-Saving Microwave-Assisted Solid-State Synthesis of Pr(3+)-, Eu(3+)-, or Tb(3+)-Doped Lu2O3 Persistent Luminescence Materials.

Persistent luminescence materials Lu2O3:R(3+),M (Pr,Hf(IV); Eu; or Tb,Ca(2+)) were successfully and rapidly (22 min) prepared by microwave-assisted solid-state synthesis (MASS) using a carbon microwave susceptor and H3BO3 as flux. Reaction times are reduced by up to 93% over previous synthetic methods, without special gases application and using a domestic microwave oven. All materials prepared with H3BO3 flux exhibit LuBO3 impurities that were quantified by Rietveld refinement from synchrotron radiation X-ray powder diffraction patterns. The flux does not considerably affect the crystalline structure of the C-Lu2O3, however. Scanning electron micrographs suggest low surface area when H3BO3 flux is used in the materials' synthesis, decreasing the amount of surface hydroxyl groups in Lu2O3 and improving the luminescence intensity of the phosphors. The carbon used as the susceptor generates CO gas, leading to complete reduction of Tb(IV) to Tb(3+) and partial conversion of Pr(IV) to Pr(3+) present in the Tb4O7 and Pr6O11 precursors, as indicated by X-ray absorption near-edge structure data. Persistent luminescence spectra of the materials show the red/near-IR, reddish orange, and green emission colors assigned to the 4f(n) → 4f(n) transitions characteristics of Pr(3+), Eu(3+), and Tb(3+) ions, respectively. Differences between the UV-excited and persistent luminescence spectra can be explained by the preferential persistent luminescence emission of R(3+) ion in the S6 site rather than R(3+) in the C2 site. In addition, inclusion of Hf(IV) and Ca(2+) codopants in the Lu2O3 host increases the emission intensity and duration of persistent luminescence due to generation of traps caused by charge compensation in the lattice. Photonic materials prepared by MASS with H3BO3 flux show higher persistent luminescence performance than those prepared by the ceramic method or MASS without flux. Color tuning of persistent luminescence in Lu2O3:R(3+),M provides potential applications in bioimaging as well as in solar cell sensitizers.