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.

Optimum fabrication parameters for preparing high performance SERS substrates based on Si pyramid structure and silver nanoparticles.

In this work, we propose simple and inexpensive methods to prepare micro/nano hierarchical Surface-Enhanced Raman Scattering (SERS) substrates, in which pyramid structure is created by using anisotropic wet etching of a silicon wafer and a silver thin film is deposited on these pyramid arrays by thermal evaporation. The ensemble is then annealed at 450 °C for 2 hours to form silver nanoparticles (AgNPs). The sizes and density of the pyramids and AgNPs are optimized mainly by changing the etching temperature (60-80 °C), the thickness of the Ag-film (15-45 nm) and etching time (3-10 min). The ultraviolet visible (UV-Vis) absorbance spectra show that the AgNPs formed with the 30 nm-thick film exhibit the strongest plasmonic effect. Under these conditions, the spherical AgNPs with sizes of 42-48 nm are densely distributed on the silicon micro-pyramid array. The obtained SERS signal is the strongest at the pyramid base-edge size of 7-10 µm. The enhancement factor obtained from the abamectin probe molecules is as high as 1 × 106 and the SERS substrates enable the detection of abamectin concentrations as low as 5.7 × 10-9 M. Therefore, this work provides a novel SERS substrate structure that has a high potential for use in medicine and biotechnology or as a food security sensor.