Highly efficient up-conversion green emission in Ho/Yb co-doped yttria-stabilized zirconia single crystals

Abstract

In the development of materials with valuable luminescence properties, we have used the optical floating zone method to prepare single crystals in the cubic phase of yttria-stabilized zirconia (YSZ) doped with 0.75 mol% Ho2O3 and various concentrations of Yb2O3. The influence of Yb3+ contents was determined for absorption and photoluminescence spectra, and fluorescence decay curves at room temperature. The absorption spectra consisted of several peaks that could be assigned to various transitions involving Yb3+ and Ho3+ ions, and oscillator strength parameters Ωt (t = 2, 4, 6) were determined using the Judd-Ofelt theory, along with the transition probability, lifetime, and branching ratio from the absorption and emission spectra of the crystal of YSZ co-doped with 0.75 mol% Ho2O3 and 1.5 mol% Yb2O3. The Ω2 value of ~14 × 10–20 cm2 indicates that the bonding around Ho3+ involves lower symmetry and higher covalency than in several other hosts, and the value of the ratio Ω4/Ω6 of 1.93 shows that this sample is a good candidate material for high quality laser output. Up-conversion emission spectra showed that Yb3+ doping significantly increased the emission intensity of 0.75 mol% Ho2O3 doped YSZ at green (557 nm), red (670 nm) and NIR (758 nm) wavelengths when excited by a 980 nm laser, and reached a maximum for 1.5 mol% Yb2O3. The emission at 557 nm was much sharper than that reported for nanocrystals of similar composition, where the maximum intensity was observed at 540 nm. Down-conversion PL spectra showed two prominent emission peaks at 1040 nm and 1213 nm, and the fluorescence decay curves indicate that energy transfer between Yb3+ and Ho3+ influenced the lifetime of the excited state of Ho3+ which varied with Yb2O3 concentration. Overall these results indicate that these Yb/Ho co-doped YSZ crystals have considerable potential for laser and luminescence applications.