Controllable structural and optical properties of NaYF4:Tm, Yb microparticles by Yb3+ doping for anti-counterfeiting.

Hexagonal NaYF4:Tm, Yb upconversion (UC) phosphors with excellent UC luminescence quantum efficiency and chemical stability meet demands for applications in bioimaging and anti-counterfeiting printing. In this work, a series of NaYF4:Tm, Yb upconversion microparticles (UCMPs) with different concentrations of Yb were synthesized by a hydrothermal method. Then, the UCMPs become hydrophilic through surface oxidation of the oleic acid (C-18) ligand to azelaic acid (C-9) using the Lemieux-von Rodloff reagent. The structure and morphology of UCMPs were investigated by X-ray diffraction and scanning electron microscopy. The optical properties were studied using diffusion reflectance spectroscopy and photoluminescent spectroscopy under 980 nm laser irradiation. The emission peaks of the Tm3+ ions are 450, 474, 650, 690, and 800 nm, attributed to the transitions from the excited state to ground state 3H6. These emissions are the results of two or three photon absorption through multi-step resonance energy transfer from excited Yb3+, confirmed via a power-dependent luminescence study. The results show that the crystal phases and luminescence properties of the NaYF4:Tm, Yb UCMPs are controlled by changing the Yb doping concentration. The printed patterns are readable under the excitation of a 980 nm LED. Moreover, the zeta potential analysis shows that the UCMPs after surface oxidation are water dispersible. In particular, the naked eye can observe the enormous upconversion emissions in UCMPs. These findings indicated that this fluorescent material is an ideal candidate for anti-counterfeiting and biological applications.

Novel Sol-Gel Route to Prepare Eu3+-Doped 80SiO2-20NaGdF4 Oxyfluoride Glass-Ceramic for Photonic Device Applications.

Oxyfluoride glass-ceramics (OxGCs) with the molar composition 80SiO2-20(1.5Eu3+: NaGdF4) were prepared with sol-gel following the "pre-crystallised nanoparticles route" with promising optical results. The preparation of 1.5 mol % Eu3+-doped NaGdF4 nanoparticles, named 1.5Eu3+: NaGdF4, was optimised and characterised using XRD, FTIR and HRTEM. The structural characterisation of 80SiO2-20(1.5Eu3+: NaGdF4) OxGCs prepared from these nanoparticles' suspension was performed by XRD and FTIR revealing the presence of hexagonal and orthorhombic NaGdF4 crystalline phases. The optical properties of both nanoparticles' phases and the related OxGCs were studied by measuring the emission and excitation spectra together with the lifetimes of the 5D0 state. The emission spectra obtained by exciting the Eu3+-O2- charge transfer band showed similar features in both cases corresponding the higher emission intensity to the 5D0→7F2 transition that indicates a non-centrosymmetric site for Eu3+ ions. Moreover, time-resolved fluorescence line-narrowed emission spectra were performed at a low temperature in OxGCs to obtain information about the site symmetry of Eu3+ in this matrix. The results show that this processing method is promising for preparing transparent OxGCs coatings for photonic applications.