用于宽范围光谱测温的Ce3+，Mn2+共掺磷酸盐双波长发射比率型荧光温度传感材料

Temperature (T) is probably the most fundamental parameter in all kinds of science. Respective sensors are widely used in daily life. Optical sensors for T, in contrast to conventional thermometers, possess the unique advantage of high sensitivity, good spatial resolution, contactless measurement and real-time imaging. As a new kind of luminescent thermometer, dual-emitting temperature sensors overcome many of the obstacles encountered with absolute intensity-based luminescence sensors, including optical occlusion, concentration variation, or nonspecificity, by providing internally referenced (ratiometric) signals. In this proposal, ratiometric and colorimetric luminescent thermometer based on Ce3+, Mn2+ co-doped phosphate dual-emitting phosphors (Ca10M(PO4)7: Ce3+, Mn2+ (M = Li, Na, K)) will be investigated. The luminescent properties could be controlled by changing Ce3+/Mn2+ ratio and the host composition. Self-calibrated luminescent temperature detecting is realized by using the regular variation of temperature-dependent emission intensity ratios of ICe3+/IMn2+. In-depth researches on structure-property relationship between host composition, structure and the corresponding luminescent properties, especially temperature-dependent luminescent properties will be applied. The energy transfer mechanism and luminescent temperature sensing mechanism will be discussed based on decay lifetimes analysis. The goal of this proposal is to explore the dual-emitting ratiometric temperature sensing materials with intense luminescence, wide temperature range and high sensitivity. As an applied fundamental research of functional-oriented novel inorganic solid-state materials, this proposal will have important academic significance and promising application potential.

荧光光谱测温有响应快、精度高、实时成像、非接触测量等优势，荧光温度传感材料可广泛应用于日常生活、科学研究和工业领域。利用双发射峰荧光强度比值与温度之间的变化关系来探测温度的比率型荧光温度传感技术，具有自校准、灵敏度高等优点。本项目拟研究基于Ce3+-Mn2+双波长发射的比率型荧光温度传感材料。制备Ce3+, Mn2+共掺的Ca10M(PO4)7 (M = Li, Na, K)磷酸盐荧光材料，通过调节基质组分和掺杂离子比例，实现对荧光性质的精确调控，利用荧光强度比值（ICe3+/IMn2+）随温度的规律变化来实现自校准荧光温度探测；深入研究基质组分结构与材料发光性质（常温/变温光谱、能量传递/荧光温度传感机理）之间的组分-结构-性质关系；最终获得宽测量范围、高灵敏度的双波长发射比率型荧光温度传感材料。本项目属于功能导向的新型无机固体材料合成与应用基础研究，具有明确应用前景和重要学术意义。

荧光光谱测温有响应快、精度高、实时成像、非接触测量等优势，荧光温度传感材料可广泛应用于日常生活、科学研究和工业领域。利用双发射峰荧光强度比值与温度之间的变化关系来探测温度的比率型荧光温度传感技术，具有自校准、灵敏度高等优点。本项目研究基于双波长发射的比率型荧光温度传感材料。通过高温固相法合成了(Ca,Sr)10Li(PO4)7:Ce3+,Mn2+固溶体荧光粉体系。通过变温发射光谱，我们发现随着温度升高，Ce3+蓝紫色发射峰强度逐渐降低，而Mn2+红色发射峰强度基本不变，呈现完全不同的变化规律。以Ce3+发射强度为温度探针，Mn2+发射强度为参比，对环境温度进行准确测量。实验表明，Ce3+蓝紫色发射峰积分面积和Mn2+红色发射峰积分面积的比值，在整个测试温度范围（室温-200摄氏度），和温度有着一阶线性关系。(Ca,Sr)10Li(PO4)7:Ce3+,Mn2+具有作为比例荧光测温材料的潜力。通过高温固相法合成了Eu2+,Mn2+共掺的Na3Sc2P3O12。在单一紫外波长激发下，样品的发光颜色可以通过Eu2+/Mn2+比例从蓝色向红色连续可调，荧光内量子效率高达98 %。通过变温发射光谱、变温荧光寿命和热释光谱拟合，对双发射峰的不同温度响应特性及其机理进行深入研究。由于存在缺陷-Eu2+ 5d激发态的热激活能量传递效应，Eu2+蓝光发射强度随温度升高而保持零热猝灭；但Mn2+红光发射强度则呈现明显的热猝灭现象。基于Eu2+蓝光和Mn2+红光的荧光强度比表现出了强烈的温度依赖特性，其相对灵敏度为1.6% K-1，表明Na3Sc2P3O12:Eu2+,Mn2+是潜在的测温传感材料。本项目通过调节基质组分和掺杂离子比例，实现对荧光性质的精确调控，利用荧光强度比值随温度的规律变化来实现自校准荧光温度探测；深入探讨基质组分结构与材料荧光性质，尤其是变温荧光性质的结构-性质关系，研究其能量传递机理和荧光温度传感机理；最终获得宽测量范围、高灵敏度的双波长发射比率型荧光温度传感材料。