硅铝酸盐基白光LED荧光粉的发光性能及其应用研究

发布时间：2018-07-05 09:02

  本文选题：硅铝酸盐 + 荧光粉　； 参考：《吉林大学》2016年博士论文

【摘要】：近年来,白光发光二极管由于具有高发光效率、节能、环保、使用方便和寿命长等的优点而受到广泛的关注和研究。发光二极管实现白光最普遍的方式是二极管芯片与荧光粉相结合。白光发光二极管的实现方式通常有两种方法:一种是蓝光芯片与黄色荧光粉Y3Al5O12:Ce组合,然而较高的猝灭温度和低显色性限制了其在照明领域的发展。另一种是紫外芯片与三基色荧光粉组合,这种方法可以克服以上不足并得到广泛应用。此种方法产生的白光均是由荧光粉发射复合而成,因此其具有高光效和高显色指数的优点。此外,单相多色荧光粉在其基础上可进一步提高发光效率和显色指数,因此,研发高稳定性和吸收较强紫外光的三色荧光粉或是单相多色发光荧光粉具有重大意义。在本论文中,我们合成了一系列以硅铝酸盐为基质的三色荧光粉和单相多色发光荧光粉,并研究了这些荧光粉的发光特性、能量传递及其在发光二极管器件上的应用。得到研究成果如下:1.通过高温固相法合成了新颖绿色荧光粉Ca2Mg0.5Al Si1.5O7:Eu2+。在368 nm激发下,该荧光粉可发射出峰值在525 nm左右的绿光。Eu2+离子的猝灭浓度和离子间的临界距离分别为1.5 mol%和13.40?。热活化能值为0.5432 e V,荧光粉的荧光寿命值为0.57μs。在绿色荧光粉Ca2Mg0.5Al Si1.5O7:Eu2+的基础上共掺Ce3+离子通过高温固相法合成了Ca2Mg0.5Al Si1.5O7:Ce3+,Eu2+蓝-绿色多色发光荧光粉。研究其发光性质,发射光谱中409和525 nm的两处发射峰分别归属于Ce3+和Eu2+离子的d-f电子跃迁。研究了Ce3+到Eu2+的能量传递,证明其是偶极-偶极的能量传递机理。进一步研究表明,在350 nm激发下通过改变Ce3+/Eu2+的相对掺杂浓度比例,荧光粉Ca2Mg0.5Al Si1.5O7:Ce3+,Eu2+可实现蓝-绿光多色发光,这表明该荧光粉在白光发光二极管领域具有潜在的应用价值。2.在荧光粉Ca2Mg0.5Al Si1.5O7:Ce3+,Eu2+的基础上,改变各元素的化学计量比,通过高温固相法合成了光色可调的单相荧光粉Ca2Mg0.25Al1.5Si1.25O7:Ce3+,Tb3+和Ca2Mg0.25Al1.5Si1.25O7:Ce3+,Eu2+。研究了Ce3+到Eu2+和Ce3+到Tb3+的能量传递,确定它们的能量传递机理分别为偶极-偶极和偶极-四极的机理。通过改变Ce3+/Eu2+和Ce3+/Tb3+的相对掺杂浓度比例可实现荧光粉Ca2Mg0.25Al1.5Si1.25O7:Ce3+,Eu2+/Tb3+蓝到绿光的多色发光,表明这两种荧光粉可作为白光发光二极管用光色可调荧光粉。3.采用高温固相法合成了一系列Ca2Mg0.75Al0.5Si1.75O7:Ln(Ln=Ce3+,Dy3+,Eu3+,Sm3+)的荧光粉,实现了三色光和白光发射。将已制备的荧光粉与紫外芯片相结合,封装成蓝、红和白光发光二极管器件,并对器件的发光效率、国际照明协会色度坐标、色温和显色指数等性能进行测试,结果表明这些荧光粉为可应用于白光发光二极管的红、蓝和白光荧光粉。4.合成了光色可调的单相白光荧光粉Ca20Al26Mg3Si3O68:Ce3+,Dy3+和黄-红光多色发光荧光粉Ca20Al26Mg3Si3O68:Dy3+,Eu3+,并研究其发光性质。对于荧光粉Ca20Al26Mg3Si3O68:Ce3+,Dy3+,在紫外光激发下,其发射光谱由407和577 nm两处发射峰组成,分别归属于Ce3+和Dy3+的电子跃迁。更重要的是,通过激发和发射光谱及荧光寿命证明了Ce3+到Dy3+的有效的能量传递的存在。最后,通过改变Ce3+/Dy3+的相对掺杂浓度实现该荧光粉蓝光-白光的多色发光,表明该荧光粉在白光发光二极管中具有潜在的应用价值。在Ca20Al26Mg3Si3O68:Dy3+,Eu3+体系中,对荧光粉Ca20Al26Mg3Si3O68:Dy3+和Ca20Al26Mg3Si3O68:Eu3+分别进行了X射线光电子能谱分析和位置选择性光谱的测试来验证Dy3+和Eu3+的掺杂位置。进一步证明和研究了Dy3+到Eu3+的能量传递。结果表明该荧光粉为在白光发光二极管领域具有潜在应用价值的黄-红光荧光粉。5.合成了一系列的Ln(Ln=Ce3+,Tb3+,Eu3+)分别单掺基质Ca2Mg0.5Al Si1.5O7,Ca2Mg0.25Al1.5Si1.25O7,Ca2Mg0.75Al0.5Si1.75O7和Ca20Al26Mg3Si3O68的三色荧光粉。并研究了这些荧光粉的发光性质及其在发光二极管器件上的应用。通过对比发光强度,选出发光性最优良的三色荧光粉并进行封装器件的测试,最后结果表明这些荧光粉为可应用于白光发光二极管的三色荧光粉。
[Abstract]:In recent years, white light emitting diode has been widely concerned and studied because of its advantages of high luminous efficiency, energy saving, environmental protection, convenient use and long life. The most common way to realize white light by LEDs is the combination of diode chips and phosphor. The implementation of white light diodes usually has two methods: one is blue. The optical chip is combined with the yellow phosphor Y3Al5O12:Ce, but the high quenching temperature and low chromaticity limit its development in the lighting field. The other is the combination of UV chip and three color phosphor. This method can overcome the above shortcomings and be widely used. The production of white light is made of phosphor powder. Therefore, it has the advantages of high light efficiency and high color rendering index. In addition, the single-phase polychromatic phosphor can further improve the luminous efficiency and color rendering index. Therefore, it is of great significance to develop high stability and absorption of strong ultraviolet light powder or single phase polychromatic phosphor. In this paper, we have synthesized a system The three color phosphors and single-phase polychromatic phosphor phosphors based on Aluminosilicate are listed, and the luminescence characteristics, energy transfer and their application on the light emitting diode are studied. The results are as follows: 1. the novel green fluorescent powder Ca2Mg0.5Al Si1.5O7:Eu2+. was synthesized by high temperature solid phase method under the excitation of 368 nm. The fluorescence powder can emit the quenching concentration of the green light.Eu2+ ion with a peak of about 525 nm and the critical distance between the ions is 1.5 mol% and 13.40? The thermal activation energy is 0.5432 e V, and the fluorescence lifetime value of the phosphor is 0.57 U S. on the basis of the green phosphor Ca2Mg0.5Al Si1.5O7:Eu2+, and the Ce3+ ions are synthesized by the high temperature solid state method. 2Mg0.5Al Si1.5O7:Ce3+, Eu2+ blue green polychromatic phosphor. Study its luminescence properties. The two emission peaks of 409 and 525 nm in emission spectra belong to d-f electron transition of Ce3+ and Eu2+ ions respectively. The energy transfer of Ce3+ to Eu2+ is studied. It is proved that it is the energy transfer mechanism of dipole dipole. Further research shows that it is excited under 350 nm. By changing the ratio of relative doping concentration of Ce3+/Eu2+, phosphor Ca2Mg0.5Al Si1.5O7:Ce3+, Eu2+ can realize blue green light polychromatic luminescence, which shows that the phosphor has potential application value in the field of white light emitting diode (.2.), on the basis of phosphor Ca2Mg0.5Al Si1.5O7:Ce3+, Eu2+, change the chemometric ratio of each element, through high temperature. The solid phase method has synthesized a light colored single-phase phosphor Ca2Mg0.25Al1.5Si1.25O7:Ce3+, Tb3+ and Ca2Mg0.25Al1.5Si1.25O7:Ce3+. Eu2+. studies the energy transfer of Ce3+ to Eu2+ and Ce3+ to Tb3+, and determines that their energy transfer mechanism is the mechanism of dipole dipole and dipole quadrupole respectively. By changing the relative concentration of Ce3+/Eu2+ and Ce3+/Tb3+, the relative doping concentration of Ce3+/Eu2+ and Ce3+/Tb3+ is changed. The ratio can realize phosphor Ca2Mg0.25Al1.5Si1.25O7:Ce3+, Eu2+/Tb3+ blue to green light, which shows that the two phosphors can be used as white light emitting diodes with light color tunable phosphor.3. to synthesize a series of Ca2Mg0.75Al0.5Si1.75O7:Ln (Ln=Ce3+, Dy3+, Eu3+, Sm3+) Phosphors by high temperature solid phase method, and realize the three color light and white. Light emission. The prepared phosphors are combined with UV chips and packaged into blue, red and white light emitting diodes. The luminescence efficiency of the devices, the chromaticity coordinates of the International Lighting Association, color temperature and color rendering index are tested. The results show that these phosphors are red, blue and white light phosphors that can be used in white light emitting diodes. .4. syntheses the light color adjustable single-phase white phosphor Ca20Al26Mg3Si3O68:Ce3+, Dy3+ and yellow red light polychromatic phosphor Ca20Al26Mg3Si3O68:Dy3+, Eu3+, and study its luminescence properties. The emission spectra of phosphor Ca20Al26Mg3Si3O68:Ce3+, Dy3+, under ultraviolet light, are composed of 407 and 577 nm two emission peaks, belonging to Ce3+, respectively. More importantly, the existence of effective energy transfer from Ce3+ to Dy3+ is demonstrated by excitation and emission spectra and fluorescence lifetime. Finally, the polychromatic luminescence of the phosphor white light is realized by changing the relative doping concentration of the Ce3+/Dy3+, which indicates that the phosphor has potential applications in the white light emitting diode. Value. In the Ca20Al26Mg3Si3O68:Dy3+, Eu3+ system, the X ray photoelectron spectroscopy and the position selective spectra of the phosphor Ca20Al26Mg3Si3O68:Dy3+ and Ca20Al26Mg3Si3O68:Eu3+ were tested to verify the doping position of Dy3+ and Eu3+. The energy transfer of Dy3+ to Eu3+ was further proved and studied. The results showed that the phosphor was the powder. A series of Ln (Ln=Ce3+, Tb3+, Eu3+) mixed with Ca2Mg0.5Al Si1.5O7, Ca2Mg0.25Al1.5Si1.25O7, Ca2Mg0.75Al0.5Si1.75O7 and Ca20Al26Mg3Si3O68 were synthesized in the yellow red light phosphor.5., which is of potential value in the field of white light emitting diodes. The luminescence properties of these phosphors and their luminescence are studied. The application of the diode device. By comparing the luminescence intensity, the best luminescent three color phosphors are selected and the test of the packaging devices is carried out. Finally, the results show that these phosphors are three color phosphors which can be used in white light emitting diodes.
【学位授予单位】：吉林大学
【学位级别】：博士
【学位授予年份】：2016
【分类号】：TN312.8;TQ422
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本文编号：2099687