Precipitation of Eu3+ - Yb3+ Codoped ZnAl2O4 Nanocrystals on Glass Surface by CO2 Laser Irradiation

We present a novel and simple method to enable spatially selective $ZnAl_2O_4$ nanocrystal formation on the surface of $B_2O_3$-$Al_2O_3$-ZnO-CaO-$K_2O$ glass by employing localized laser heating. Optimized precipitation of glass-ceramics containing nanocrystals doped with $Eu^{3+}$ and $Yb^{3+}$ ions was performed by controlling $CO_2$ laser power and scan speed. Micro-x-ray diffraction and transmission electron microscopy revealed the mean size and morphology of nanocrystals, and energy dispersive x-ray spectroscopy showed the lateral distribution of elements in the imaged area. Laser power and scan speed controled annealing temperature for crystalization in the range of 1.4-1.8 W and 0.01-0.3 mm/s, and changed the size of nanocrystals and distribution of dopant ions. We also report more than 20 times enhanced downshift visible emission under ultraviolet excitation, and 3 times increased upconversion emission from $Eu^{3+}$ ions assisted by efficient sensitizer $Yb^{3+}$ ions in nanocrystals under 980 nm excitation. The confocal microscope revealed the depth profile of $Eu^{3+}$ ions by showing their emission intensity variation.