Luminescent materials with dual-mode excitation and tunable emission color for anti-counterfeiting applications.

GdVO4-based dual-mode phosphors were successfully synthesized via a hydrothermal approach. The X-ray diffraction analysis determined the tetragonal structure as well as I41/amd space group of products by comparing with a reference pattern no. ICDD #01-072-0277. The morphology of yielded phosphors was confirmed by transmission electron microscopy and scanning electron microscopy. Detailed spectroscopy analysis revealed tunable luminescence properties with an increasing Yb3+ content in series of GdVO4: x% Yb3+, y% Tm3+, 5% Eu3+ (x = 5, 10, 15, 20; y = 0.1, 0.5, 1) phosphors. For Yb3+, Tm3+, and Eu3+- codoped phosphors we observed bands related to the 1G4 → 3H6 and 1G4 → 3F4 transitions of Tm3+ ions, occurred through the cooperative up-conversion mechanism, where two nearby Yb3+ ions were involved in near-infrared absorption. Moreover, the GdVO4: 20% Yb3+, 0.5% Tm3+, 5% Eu3+ showed the most outstanding color tunability from red color (x = 0.6338, y = 0.3172) under UV to blue color (x = 0.2640, y = 0.1988) under NIR excitation, which can be applied in anti-counterfeiting activity.

Multifunctional cellulose fibers: Intense red upconversion under 1532 nm excitation and temperature-sensing properties.

The unique properties of upconverting nanoparticles are responsible for their various applications in photonic materials, medicine, analytics, or energy conversion. In this work, the NaErF4:Tm3+@NaYF4 core@shell nanoparticles were synthesized by reaction in high-boiling point solvents and incorporated into cellulose fibers. Nanoparticles showed intense upconversion under 1532 nm excitation wavelength due to Er3+ in their structure. Additional co-doping with Tm3+ ions allowed to shift of the typical green luminescence of Er3+ ions to red especially demanded in anti-counterfeiting applications. The products' composition, morphology, and structure parameters confirmed their requested properties. The article demonstrates that cellulose fibers are suitable carriers of NaErF4:Tm3+@NaYF4 NPs. We also show that the temperature-dependent emission of Er3+ ions allows for the preparation of temperature-sensing cellulose fibers.

New Multicolor Tungstate-Molybdate Microphosphors as an Alternative to LED Components.

Due to the ongoing need to create phosphors with the appropriate emission color for the production of light emitting diodes, we decided to synthesize a series of multicolour microphosphors with tunable visible emissions, depending on the composition of dopant ions. In this work, we investigated the structure, morphology, and luminescent properties of new molybdate-tungstate phosphors co-doped with Tb3+ and Eu3+ ions. The conventional high temperature solid state method was used to prepare a series of CaMoyW1-yO4:Eu3+x/Tb3+1-x materials. In order to obtain phosphors with the most promising luminescent properties, the experiment was planned by taking into account the different composition of the matrix and the concentration of the particular dopant ions (Eu3+x/Tb3+1-x, x = 0.001, 0.003, 0.005, 0.007, 0.009). As a result, luminescent materials were obtained with a pure tetragonal crystal structure, the space group of I41/a, confirmed by X-ray diffraction (XRD). The size and shape of the particles obtained from the materials were analyzed based on scanning electron microscopy images. Luminescence spectroscopy (excitation and emission spectra, decay lifetimes) was utilized to characterize the luminescence properties of the as-prepared phosphors. The color change of the emission from green-yellow to orange-red was confirmed using the 1931 Comission Internationale de l'Eclairage (CIE) chromaticity coordinates and color correlated temperature (CCT).

Influence of GdVO4:Eu3+ Nanocrystals on Growth, Germination, Root Cell Viability and Oxidative Stress of Wheat (Triticum aestivum L.) Seedlings.

The increasing application of lanthanide-doped nanocrystals (LDNCs) entails the risk of a harmful impact on the natural environment. Therefore, in the presented study the influence of gadolinium orthovanadates doped with Eu3+ (GdVO4:Eu3) nanocrystals on wheat (Triticum aestivum L.), chosen as a model plant species, was investigated. The seeds were grown in Petri dishes filled with colloids of LDNCs at the concentrations of 0, 10, 50 and 100 µg/mL. The plants' growth endpoints (number of roots, roots length, roots mass, hypocotyl length and hypocotyl mass) and germination rate were not significantly changed after the exposure to GdVO4:Eu3+ nanocrystals at all used concentrations. The presence of LDNCs also had no effect on oxidative stress intensity, which was determined on the basis of the amount of lipid peroxidation product (thiobarbituric acid reactive substances; TBARS) in the roots. Similarly, TTC (tetrazolium chloride) assay did not show any differences in cells' viability. However, root cells of the treated seedlings contained less Evans Blue (EB) when compared to the control. The obtained results, on the one hand, suggest that GdVO4:Eu3+ nanocrystals are safe for plants in the tested concentrations, while on the other hand they indicate that LDNCs may interfere with the functioning of the root cell membrane.

Spectroscopic, structural and in vitro cytotoxicity evaluation of luminescent, lanthanide doped core@shell nanomaterials GdVO4:Eu(3+)5%@SiO2@NH2.

The luminescent GdVO4:Eu(3+)5%@SiO2@NH2 core@shell nanomaterials were obtained via co-precipitation method, followed by hydrolysis and co-condensation of silane derivatives: tetraethyl orthosilicate and 3-aminopropyltriethoxysilane. Their effect on human erythrocytes sedimentation and on proliferation of human lung microvascular endothelial cells was examined and discussed. The luminescent nanoparticles were synthesized in the presence of polyacrylic acid or glycerin in order to minimalize the agglomeration and excessive growth of nanostructures. Surface coating with amine functionalized silica shell improved their biocompatibility, facilitated further organic conjugation and protected the internal core. Magnetic measurements revealed an enhanced T1-relaxivity for the synthesized GdVO4:Eu(3+)5% nanostructures. Structure, morphology and average grain size of the obtained nanomaterials were determined by X-ray diffraction, transmission electron microscopy and dynamic light scattering analysis. The qualitative elemental composition of the nanomaterials was established using energy-dispersive X-ray spectroscopy. The spectroscopic characteristic of red emitting core@shell nanophosphors was completed by measuring luminescence spectra and decays. The emission spectra revealed characteristic bands of Eu(3+) ions related to the transitions (5)D0-(7)F0,1,2,3,4 and (5)D1-(7)F1. The luminescence lifetimes consisted of two components, associated with the presence of Eu(3+) ions located at the surface of the crystallites and in the bulk.

Synthesis, characterization, and cytotoxicity in human erythrocytes of multifunctional, magnetic, and luminescent nanocrystalline rare earth fluorides.

Multifunctional nanoparticles exhibiting red or green luminescence properties and magnetism were synthesized and thoroughly analyzed. The hydrothermal method was used for the synthesis of Eu3+- or Tb3+-doped GdF3-, NaGdF4-, and BaGdF5-based nanocrystalline materials. The X-ray diffraction patterns of the samples confirmed the desired compositions of the materials. Transmission electron microscope images revealed the different morphologies of the products, including the nanocrystal sizes, which varied from 12 nm in the case of BaGdF5-based nanoparticles to larger structures with dimensions exceeding 300 nm. All of the samples presented luminescence under ultraviolet irradiation, as well as when the samples were in the form of water colloids. The highest luminescence was observed for BaGdF5-based materials. The obtained nanoparticles exhibited paramagnetism along with probable evidence of superparamagnetic behavior at low temperatures. The particles' magnetic characteristics were also preserved for samples in the form of a suspension in distilled water. The cytotoxicity studies against the human erythrocytes indicated that the synthesized nanoparticles are non-toxic because they did not cause the red blood cells shape changes nor did they alter their membrane structure and permeabilization.

Synthesis and spectroscopic properties of Yb3+ and Tb3+ co-doped GdBO3 materials showing down- and up-conversion luminescence.

Gadolinium orthoborates doped with Yb(3+) and Tb(3+) ions were synthesised by the sol-gel Pechini method. Materials annealed at 900 °C were composed of the monoclinic GdBO3 phase with micrometre-sized crystals. The structural properties of the products were analysed by X-ray diffraction (XRD) and transmission electron microscopy (TEM). The composition of the prepared materials was determined by inductively coupled plasma optical emission spectroscopy (ICP-OES). The materials showed intense ultraviolet (UV) or near infrared (NIR) excited green emission, which resulted from down- or up-conversion processes taking place in their structure. Spectroscopic properties were investigated on the basis of the measured excitation and emission spectra. Also, luminescence decays showing a short rise of emission with time after NIR excitation were measured. The dependence of the integral up-conversion intensity on the energy of the pumping laser was measured. The results indicated a two-photon process based on cooperative energy transfer (CET). The analysis of the synthesised series of samples allowed us to identify those with the best emission under a UV or NIR excitation source.

Structural, spectroscopic, and magnetic properties of Eu3+-doped GdVO4 nanocrystals synthesized by a hydrothermal method.

New interesting aspects of the spectroscopic properties, magnetism, and method of synthesis of gadolinium orthovanadates doped with Eu(3+) ions are discussed. Gd(1-x)Eu(x)VO4 (x = 0, 0.05, 0.2) bifunctional luminescent materials with complex magnetic properties were synthesized by a microwave-assisted hydrothermal method. Products were formed in situ without previous precipitation. The crystal structures and morphologies of the obtained nanomaterials were analyzed by X-ray diffraction and transmission and scanning electron microscopy. Crystallographic data were analyzed using Rietveld refinement. The products obtained were nanocrystalline with average grain sizes of 70-80 nm. The qualitative and quantitative elemental composition as well as mapping of the nanocrystals was proved using energy-dispersive X-ray spectroscopy. The spectroscopic properties of red-emitting nanophosphors were characterized by their excitation and emission spectra and luminescence decays. Magnetic measurements were performed by means of vibrating sample magnetometry. GdVO4 and Gd0.8Eu0.2VO4 exhibited paramagnetic behavior with a weak influence of antiferromagnetic couplings between rare-earth ions. In the substituted sample, an additional magnetic contribution connected with the population of low-lying excited states of europium was observed.

Hydrothermal synthesis and structural and spectroscopic properties of the new triclinic form of GdBO3:Eu3+ nanocrystals.

Triclinic Gd1-xEuxBO3 nanophosphors have been prepared by a hydrothermal method without using additional coreagents and prior precipitation of precursor (in situ). The formation of the borate nanorods and their crystal structure was refined on the basis of X-ray diffraction patterns (XRD) and well confirmed using various techniques such as infrared spectroscopy (IR), Raman spectroscopy, transmission electron microscopy (TEM), and energy-dispersive X-ray spectroscopy (EDX). The new triclinic crystal structure (space group P1) for the GdBO3 nanocrystals and detailed structure parameters were determined with the help of the Rietveld analysis. The spectroscopic characteristics of the synthesized nanomaterials with different concentrations of Eu(3+) ions were defined with the use of luminescence excitation spectra as well as emission spectra and decay kinetics. The Judd-Ofelt parameters (Ω2, Ω4) and quantum efficiency, η, were also calculated for the more detailed analysis of Eu(3+) spectra in the GdBO3 host.

Revision of structural properties of GdBO3 nanopowders doped with Eu3+ ions through spectroscopic studies.

Monoclinic Gd(1-x)Eu(x)BO(3) nanopowders were successfully synthesized using a modified Pechini method. The crystal structure of the prepared materials was revised and confirmed using several techniques such as: IR, XRD, TEM, Raman spectroscopy and EDX analysis. The obtained material was comprised of particles, consisting of parts with the average size 350 nm. The luminescence properties of the prepared phosphors with different concentrations of Eu(3+) ions were characterized by excitation and emission spectra and its kinetic decay. The Judd-Ofelt parameters (Ω(2), Ω(4)), quantum efficiency, η, and chromaticity coordinates were also calculated.