白光LEDs用颜色可调型硅酸盐及磷酸盐荧光粉的设计、合成及性能研究

发布时间：2018-03-25 21:04

本文选题：荧光粉　切入点：Ca_(0.75)Sr_(0.2)Mg_(1.05)(Si_2O_6)　出处：《河北大学》2017年硕士论文

【摘要】：本文以 Ca0.75Sr0.2Mg1.05(Si2O6)(CSMS)和 Ba2Ca(PO4)2(BCPO)为基质,利用传统的高温固相法制备了一系列新的 CSMS、CSMS:Eu2+,Mn2+、Ba2Ca1-xMx(PO4)2:Eu2+(M=Mg,Sr,Zn)等荧光发光材料。对基质晶格的缺陷发光,基质与掺杂离子间、掺杂离子与掺杂离子间的能量传递,多阳离子取代造成的荧光发射光谱反向红蓝移以及温度光谱的能量反传递等现象进行了细致地研究与讨论:(1)Ca0.75Sr0.2Mg1.05(Si2O6)基质荧光材料在高温固相还原反应下合成,并从晶体结构、基质激发的发光过程、温度特性曲线等方面对基质的缺陷发光进行了细致地分析。该基质在紫外灯的照射下呈现为橘黄色,通过荧光光谱测量,CSMS基质的发射带有两个明显的发射峰,分别位于453 nm和580 nm,波长大致在350 nm-800 nm范围内。监测基质的温度特性,可以看到,随着温度的上升,发射光谱出现不同程度的蓝移、红移和强度变化。(2)利用高温固相法,制备了颜色可调型Ca0.75-xSr0.2Mg1.05-y(Si2O6):xEu2+,yMn2+荧光粉。文中详细分析了材料的荧光光谱、色坐标、量子效率、热释光谱、漫反射光谱、荧光寿命衰减曲线。对CSMS:xEu2+,半峰宽为41nm,发射波长为200-450 nm,发射主峰在453 nm,大量子效率可达66.08%,色坐标为(0.1451,0.0736),属于典型的蓝光发射。对CSMS:yMn2+荧光粉,激发波长为415nm,发射主峰为680 nm,呈浅红色。对 Ca0.75-xSr0.2Mg1.05-y(Si2O6):xEu2+,yMn2+样品,证明了 Eu2+→Mn2+,Eu2+→基质,基质→Mn2+间的能量传递关系,使CSMS:0.03Eu2+,0.02Mn2+荧光粉呈现蓝白光发射,色坐标为(0.2682,0.2056)。(3)通过在Eu2+激活的Ba2Ca(PO4)2基质中引入新的阳离子(Mg,Sr,Zn),制备了一系列Ba2Ca1-xMx(PO4)2:Eu2+(M=Mg,Sr,Zn)新型荧光粉。文中,对基质中组分中含有不只一个阳离子的基质提出了一种掺杂离子(Eu2+)“直接取代和间接取代”的新机理,同时对具有多个发光中心的基质提出了“选择激发”的概念。随着样品颜色从蓝色到黄色的调控,在Ba2Ca1-xMgx(PO4)2:Eu2+体系的发射光谱中观测到了反常的红移现象(479→602 nm),而在Ba2Ca1-ySry(PO4)2:Eu2+体系中,观测到光谱的发射主波长向短波方向移动(485→441 nm)。对Ba2Ca1-zZnz(PO4)2:Eu2+,激发在355 nm时,光谱先蓝移,然后红移;当激发为400 nm时,光谱连续红移。此外,当引入一种新的阳离子时较大比例的改变基质组分时,文中认为新基质合成的的过程中大体上会经过三种物态的存在方式:固溶体态、混合物态、新物质。对Ba2Ca1-zZnz(PO4)2:Eu2+(y=0.7,0.8,09),随温度升高,谱型开始转变。通过对该系列光谱的进行高斯分峰拟合,证明了在不同的Eu2+的发光中心存在能量传递以及热释能量的反向传递的现象。最后,本文用实验制备的 Ba2Ca0.7Mg0.3(PO4)2:Eu2+和 Ba2Ca0.3Sr0.7(PO4)2:Eu2+样品辅以380 nm的LED芯片进行封装,得暖白光发射。
[Abstract]:Using Ca0.75Sr0.2Mg1.05Si2O6 (CSMSS) and Ba2CaOPO4O2BCPO) as substrates, a series of new luminescent materials, such as CSMS: CSMS: EU2, Mn2, Ba2Ca1-xMxPO4, EU2: EU2MMgSrOZnZn), have been prepared by conventional high temperature solid state method. The luminescence of the matrix crystal lattice, the luminescence between the substrate and the doped ions, and so on, have been studied. The energy transfer between doped ions and doped ions, The reverse red-blue shift of fluorescence emission spectrum caused by polycation substitution and the energy back transfer of temperature spectrum were studied and discussed in detail. The synthesis of the fluorescent matrix material of 1: 1 Ca-0.75Sr0.2Mg1.05Si2O6) was carried out under the solid state reduction reaction at high temperature, and the structure of the substrate was obtained from the crystal structure. The luminescence process induced by the substrate, temperature characteristic curve and so on, were analyzed in detail. The luminescence of the substrate was orange under the irradiation of ultraviolet lamp. Fluorescence spectra were used to measure the emission of CSMS matrix with two distinct emission peaks, located at 453nm and 580nm, respectively, and the wavelength was approximately 350 nm-800 nm. Monitoring the temperature characteristics of the substrate, we can see that with the increase of temperature, Blue shift, red shift and intensity change of emission spectra.) the color adjustable Ca0.75-xSr0.2Mg1.05-y(Si2O6):xEu2 yMn2 phosphors were prepared by high temperature solid state method. The fluorescence spectra, chromatic coordinates, quantum efficiency and thermoluminescence spectra of the phosphors were analyzed in detail. Diffuse reflectance spectrum, fluorescence lifetime attenuation curve. For CSMS:xEu2, the half peak width is 41 nm, the emission wavelength is 200-450 nm, the main emission peak is 453 nm, the mass efficiency can reach 66.08 and the color coordinate is 0.1451 ~ 0.0736, which belongs to the typical blue emission. The excitation wavelength is 415nm, the main emission peak is 680nm, which is light red. For the sample of Ca0.75-xSr0.2Mg1.05-y(Si2O6):xEu2 yMn2, it is proved that Eu2. 鈫扢n2 ,Eu2. 鈫扢atrix. 鈫扵he energy transfer relationship between Mn2 makes CSMS:0.03Eu2 _ (0.02Mn _ 2) phosphors appear blue and white emission. The color coordinate is 0.2682 ~ 0.2056 ~ (5).) A series of new phosphors of Ba2Ca1-xMx(PO4)2:Eu2 _ (M _ (M)) _ (mg ~ (2 +)) SrZn) have been prepared by introducing a new cationic cation (Eu2) to the Ba2Ca(PO4)2 substrate activated by Eu2. A new mechanism of "direct substitution and indirect substitution" was proposed for the matrix containing more than one cation in the matrix. At the same time, the concept of "selective excitation" was proposed for the matrix with multiple luminous centers. With the regulation of the color of the sample from blue to yellow, the abnormal red-shift phenomenon was observed in the emission spectra of the Ba2Ca1-xMgx(PO4)2:Eu2 system. 鈫扞n the Ba2Ca1-ySry(PO4)2:Eu2 system, the main emission wavelength of the spectrum moved towards the shortwave direction. 鈫扚or Ba2Ca1-zZnz(PO4)2:Eu2, when excited at 355nm, the spectrum shifts first to blue, then to red; when excited to 400nm, the spectrum continuously redshifts. In addition, when a new cation is introduced, a large proportion of the matrix components are changed. In this paper, it is considered that there are three kinds of physical states in the process of synthesis of new substrates: solid solution state, mixture state, new substance. The spectral pattern is beginning to change. By fitting the spectrum with Gao Si, it is proved that there is energy transfer and reverse transfer of thermoluminescence energy in different Eu2 luminescence centers. In this paper, the experimental Ba2Ca0.7Mg0.3(PO4)2:Eu2 and Ba2Ca0.3Sr0.7(PO4)2:Eu2 samples were encapsulated with a 380nm LED chip to obtain warm white light emission.
【学位授予单位】：河北大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：TQ422;TN312.8

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