The Preparation And Luminescent Properties Of Rare Earth Doped The Glass/Glass Ceramics Of Fluoride Zirconate

Because of better physical and chemical properties, fluorine-zirconate glass matrix, withlow phonon energy (only560cm-1) and high dopant solubility, is considered to be the mainfluorescent material. It illustrates the active application in display and lighting, optical fiberlaser and optical fiber communication etc. In this dissertation, the white-light emissionmechanism for the Tm3+-Tb3+-Eu3+triply-doped ZrF4-BaF2-LaF3-AlF3-NaF (ZBLAN) glasswas discussed based on the energy transfer process between Tb3+to Eu3+. The microcrystallinecondition in glass matrix and thermal stability were also concerned. The main results are asfollows:(1) The Tm3+-Tb3+-Eu3+triply-doped ZBLAN transparent glasses were synthesized bymelt-quenching method. Under excitation of365nm, the white emission was observed incombination by the red, green and blue band simultaneously. The CIE (CommissionInternationale deL’Eclairage) coordinates were tuned from (x=0.276, y=0.29) to (x=0.337,y=0.337) with the Eu3+concentration from0.5mol%to1.2mol%. The standard white CIEcoordinates of (0.332,0.330) was achieved at the Eu3+concentration of1.1mol%. The energytransfer process between Tb3+to Eu3+under excitation of365nm was discussed in terms ofthe photoluminescence excitation (PLE) spectra and the light emission decay curves.(2) The emission spectra of Tm3+/Tb3+/Eu3+single-doped and triply-doped ZBLANtransparent glasses in blue (450nm), green (541nm) and red (611nm) band were discussedunder influence by temperature. The thermal quenching rates for three bands were owed to thedifferent thermal activation energy of Tm3+, Tb3+and Eu3+. With the temperture increase, theemission color of triply-doped ZBLAN shifted from white to blue.(3) ZBLAN transparent glass ceramic microcrystalline was prepared with precursorsBaF2replaced by BaCl2. The nucleation and crystallization temperature were confirmed at294℃and424℃by Differential Thermal Analysis (DTA). The emission intensity withEu3+-doped was enhanced by heat treatment process. The concentration quenching was alsoinvolved with increase of Eu3+doping concentration.