ZBLAN玻璃中Nd~(3+),Tm~(3+),Yb~(3+)的上转换发光特性

采用高温固相法制备了Nd,Tm和Yb掺杂的ZBLAN玻璃上转换材料.Tm3+,Yb3+的摩尔浓度分别固定为0.01%,0.3%,Nd3+摩尔浓度变化范围为0.1%～2%.在室温下,测试了样品在300～1 000nm间的吸收光谱.在798 nm近红外光激发下,测试了样品的上转换光谱.实验发现,样品在798 nm红外光激发下发出了较强的多波段(红,蓝和绿)的可见光.由上转换可见光各波段的发射谱线,给出了能级跃迁机制.蓝光主要来源于Tm3+的激发态1G4到基态3H6的跃迁,绿光来源于Nd3+的2H7/2到基态4I9/2的跃迁,红光来源于Nd3+的2H11/2到基态4i9/2的跃迁.研究发现,在Nd3+,Tm3+,Yb3+:ZBLAN玻璃样品中存在激发态吸收,能最转移和交叉弛豫等上转换过程.其发光机理是Nd3+,TM3+和Yb3+离子之间的能量转移.根据Nd3+摩尔浓度不同其上转换发光强度不同,分析了掺入稀土的浓度对上转换发光效率的影响.当Nd3+浓度为1.5%(摩尔分数)时上转换发光最强,大于1.5%后发光开始减弱.

Upconversion Luminescence Properties of ZBLAN:Nd3+,Tm3+,Yb3+

The ZBLAN∶Nd3+, Tm3+, Yb3+ upconversion materials were prepared by high-temperature solid method. The concentrations of Tm3+ and Yb3+ were 0.01% and 0.3% respectively. The concentration of Nd3+ changed in the range from 0.1% to 2%. The absorption spectrum of ZBLAN∶Nd3+, Tm3+, Yb3+ in all samples from 300 to 1 000 nm was measured at room temperature. The upconversion emission was observed when excited by 798 nm infrared light. The material samples emitted relatively strong multi-band (the red, blue and green color) visible light. Based on the experiment, the multi-band visible spectral lines were analyzed, and the energy level transition mechanism was given. The blue light results from the transition of 1G4→3H6 of Tm3+, the green light is from the transition of 2H7/2→4I9/2 of Nd3+, and the red light originates from the transition of 2H11/2→4I9/2 of Nd3+. The results show that the upconversion mechanism includes excited state absorption, energy transfer, cross relaxation and so on. The energy transfer processes between Nd3+, Tm3+ and Yb3+ ions both forward and backward prove to be the origin of upconversion emissions. The effect of rare earth doping concentration on the energy upconversion efficiency was analyzed, according to the different upconversion light emitting intensity from samples with different Tm3+ mol concentrations. The upconversion luminescence increased with the Nd3+ concentration and got its peak at 1.5%.