新型白光LED用玻璃陶瓷制备与发光性能研究

New luminescent glass-ceramics have a prime important application in the great martial and civil field, such as solid state lighting, color display, temperature sensor and fluorescence labeling system, etc. This material is not only new generation material having very important effects on National energy strategy and sustainable development of national economy, but also vital front direction in current field for inorganic solid-state luminescent materials science and engineering as well as its application.Based on phosphate glass system, the focus is exploring preparation technology of luminescent glass-ceramics with high efficiency and good properties, researching effects of composition, types and contents of doping ions on glass forming ability and luminescent properties, clarifying effects of heat treatment technology on phase composition, microstructure and spectral characteristics, revealing internal correlation between composition, microstructure and luminescent properties by using Raman spectra, Infrared absorption spectra and fluorescence spectra, and finding out crystallization and luminescent mechanism of multi-ion doped phosphate glass-ceramics in order to finally advance theoretical basis and practical evidence for developing novel phosphate glass-ceramic materials for white light emitting diode (WLED). Meanwhile, developing new luminescent glass-ceramic materials for WLED combined the advantages of local resources not only is in keeping with China's western development policy, but also is in favor of perpetual and healthy development of mineral economic in Guangxi.

新型发光玻璃陶瓷在固态照明、彩色显示、温度传感、荧光示踪系统等重大军民用领域都有极为重要的应用，是一类对国家能源战略和国民经济可持续发展具有重大意义的新一代材料，也是当前国际上无机固体发光材料科学与工程领域研究和应用方面的重要前沿方向。本项目以磷酸盐玻璃体系为研究对象，探索高效发光玻璃陶瓷制备技术；研究组成、掺杂离子种类和含量对玻璃形成能力和发光性能的影响；阐明热处理工艺对相组成、微结构和光谱特性的影响规律；利用拉曼、红外光谱及荧光光谱揭示材料的组成、结构与发光性能的内在关联；弄清多离子掺杂磷酸盐玻璃陶瓷的晶化与发光机理，为开发出新型白光LED用磷酸盐玻璃陶瓷材料提供理论和实践依据。同时，本项目结合地方资源优势，开展新型白光LED用发光材料的研究，符合我国西部大开发的重大方针，有利于广西矿产经济可持续健康发展。

新型发光玻璃陶瓷在固态照明、彩色显示、温度传感、荧光示踪系统等重大军、民用领域都有极为重要的应用，是一类对国家能源战略和国民经济可持续发展具有重大意义的新一代材料。本项目针对传统白光LED显色指数不高、发光效率较低和发光性能不稳定等关键问题，基于广西特色资源（稀土氧化物、氧化锌、氧化锰等），采用熔融-可控析晶技术制备系列白光LED用新型发光磷酸盐玻璃和玻璃陶瓷材料。探讨了玻璃组成(P2O5、K2O、Al2O3、B2O3、Sb2O3)对磷酸盐玻璃热稳定性、玻璃形成能力和析晶动力学的影响；弄清了单个稀土离子（Tm3+、Tb3+、Sm3+、Eu3+、Mn2+、Dy3+）在磷酸盐玻璃及玻璃陶瓷中的光谱特性和发光机理；研究了双掺离子种类（Tb3+/Eu3+、Tb3+/Sm3+、 Tm3+/Dy3+）和浓度对磷酸盐玻璃发光性能的影响及其离子间的能量转换机理；探索了三掺离子种类（Tm3+/Tb3+/Eu3+、Tm3+/Tb3+/Mn2+、Tm3+/Tb3+/Sm3+、Ce3+/Tb3+/ Mn2+）和浓度在磷酸盐玻璃中的发光特性、荧光寿命、色坐标与色温及其能量转换机制；阐明了和热处理工艺对三掺（Ce3+/Tb3+/Mn2+、Tm3+/Tb3+/Sm3+、Tm3+/Tb3+/Eu3+）磷酸盐玻璃陶瓷的相组成和荧光性能的影响。获得四种综合性能优异的白光LED 用发光玻璃及玻璃陶瓷材料。双掺0.6Tm3+/0.8Dy3+的38P2O5-44ZnO-16SrO-2ZrO2磷酸盐玻璃和玻璃陶瓷样品在353nm激发下都呈现接近标准白光的白光发射，而且玻璃陶瓷样品发射白光的强度明显比玻璃强。在357nm激发下，三掺 Tm3+/Tb3+/Sm3+和Ce3+/Tb3+/ Mn2+ 离子的析出SrZnP2O7晶体的磷酸盐玻璃陶瓷的色坐标分别为（0.3148, 0.3388）和（0.319，0310）。在362 nm激发下，掺杂1.0 mol %Tm3+ +2.0 mol%Tb3+ +0.3 mol% Eu3+的NaZnPO4透明玻璃陶瓷的色坐标和色温分别为（0.3335, 0.3430）和（5449.2K）。这些研究结果可为新型白光LED 用发光玻璃陶瓷材料的制备及其实际应用提供有重要的实验依据和理论指导。