基于能量傳遞獲取顏色可調(diào)型硼酸鹽熒光粉及其性能調(diào)控
發(fā)布時間：2019-06-19 23:37
【摘要】：本文以兩種硼酸鹽LiBaBO_3和Ba_2B_2O_5為基質(zhì),分別通過摻雜不同的稀土離子Eu~(2+)、Eu~(3+)、Tb~(3+)、Ce~(3+)、Sm~(3+)、Dy~(3+),以及過渡金屬Mn~(2+)離子,通過高溫固相法,合成了多種新型的熒光粉,并詳細地研究了合成熒光粉的各種性能。主要的研究內(nèi)容如下:(1)利用高溫固相傳統(tǒng)方法,合成了一系列LiBaBO_3:RE(RE=Eu~(2+)/Tb~(3+)/Eu~(3+))熒光粉。通過研究樣品的發(fā)射光譜、激發(fā)光譜,以及壽命衰變曲線等,發(fā)現(xiàn)在強還原的氣氛下,LiBaBO_3:Eu熒光粉表現(xiàn)出Eu~(2+)的藍綠色光,而在弱還原的氣氛下,LiBaBO_3:Eu熒光粉中,會出現(xiàn)Eu~(2+)與Eu~(3+)離子共存的現(xiàn)象。而且,在空氣中燒結(jié)LiBaBO_3:Eu,Tb樣品時,會出現(xiàn)Tb~(3+)向Eu~(3+)傳遞能量的現(xiàn)象。而在弱還原條件下,結(jié)燒Eu,Tb共摻的LiBaBO_3:樣品時,出現(xiàn)了Eu~(2+)離子,Eu~(3+)離子與Tb~(3+)離子共存的現(xiàn)象,并且會發(fā)生Eu~(2+)-Tb~(3+)-Eu~(3+)離子的能量傳遞,得到樣品的顏色,也從藍色到紅色可調(diào)。也就是說,在LiBaBO_3基質(zhì)中,Tb~(3+)離子可以作為能量傳遞的橋梁,來連接Eu~(2+)離子與Eu~(3+)離子,最終得到顏色可調(diào)的熒光粉。研究結(jié)果表明,Tb~(3+)離子可以起到為Eu~(3+)離子儲存能量的作用,而且LiBaBO_3可以作為LED可調(diào)顏色的潛在基質(zhì)。(2)利用高溫固相法,合成了一系列單相LiBaBO3:Ce~(3+),AR(R=Eu~(2+),Mn~(2+),Dy~(3+),Sm~(3+),Tb~(3+))以及LiBaBO_3:Tb~(3+),BE(E=Mn~(2+),Dy~(3+),Sm~(3+))熒光粉,并且詳細地研究了合成熒光粉的發(fā)光性能。通過具體分析得到熒光粉的各種性能,發(fā)現(xiàn)在LiBaBO_3基質(zhì)中,Ce~(3+)離子可以與共摻的Eu~(2+)/Mn~(2+)/Dy~(3+)/Sm~(3+)/Tb~(3+)離子,通過偶極-偶極的相互作用,向這些離子傳遞能量。除此之外,在LiBaBO_3基質(zhì)中,當Tb~(3+)離子與其它離子共摻時,共摻的離子會影響Tb~(3+)離子的激發(fā)光譜。最終,通過對樣品的色坐標的測定,得到了一系列顏色可調(diào)的熒光粉。結(jié)果表明,LiBaBO_3基質(zhì)在LED可調(diào)顏色的發(fā)展上,有著潛在的應用價值。(3)高溫固相法,制備了一系列Ce~(3+)/Tb~(3+)/Sm~(3+)摻雜Ba_2B_2O_5基質(zhì)的熒光粉,并且詳細的研究了得到熒光粉的發(fā)光特性。在這三種離子單獨摻雜在此基質(zhì)中時,分別表現(xiàn)出藍色,綠色,以及紅色的發(fā)光顏色。而當這三種離子中,任何兩種離子共摻雜在Ba_2B_2O_5基質(zhì)中后,Ce~(3+)離子可以向Tb~(3+)離子傳遞能量,同樣Tb~(3+)離子也可以向Sm~(3+)離子傳遞能量。但是當Ce~(3+)與Sm~(3+)離子共同摻雜在Ba_2B_2O_5基質(zhì)中,Ce~(3+)離子并不能向Sm~(3+)離子傳遞能量。而當三種離子同時摻雜在Ba_2B_2O_5基質(zhì)中以后,Tb~(3+)離子可以作為能量傳遞的橋梁,來連接Ce~(3+)離子與Sm~(3+)離子。也就是說,在Ba_2B_2O_5基質(zhì)中,通過Tb~(3+)離子的橋梁作用,實現(xiàn)了三種離子間能量傳遞的效果,并且最終得到了白色的熒光粉。實驗結(jié)果表明,Ba_2B_2O_5:Ce,Tb,Sm三摻的白色熒光粉,有應用在白色LED上的潛力。(4)利用高溫固相的傳統(tǒng)方法,在Ba_2B_2O_5:Ce熒光粉基礎上,以Sr/Ca/Mg/Zn部分取代Ba,獲得了一系列熒光粉,研究了四類熒光粉的發(fā)光特性。通過對發(fā)射光譜以及激發(fā)光譜的詳細分析,發(fā)現(xiàn)這一系列陽離子替代熒光粉的最佳激發(fā),都位于360 nm附近,并且隨著Ba離子被這四種小半徑的離子替代時,發(fā)射光譜都先發(fā)生了紅移,然后又逐漸的藍移。除此之外,得到的樣品色坐標位置,發(fā)現(xiàn)隨著Ba離子逐漸的被替代成小半徑的離子時,樣品的顏色發(fā)生了很小的改變。因此,通過實驗,得到了可以微調(diào)樣品發(fā)射顏色的一種方法。
[Abstract]:Based on the two kinds of borate LiBaBO _ 3 and Ba _ 2B _ 2O _ 5, different rare-earth ions, Eu ~ (2 +), Eu ~ (3 +), Tb ~ (3 +), Ce ~ (3 +), Sm ~ (3 +), Dy ~ (3 +), and transition metal Mn ~ (2 +), were synthesized by high-temperature solid-phase method. And the various properties of the synthesized fluorescent powder are studied in detail. The main contents of the study are as follows: (1) A series of LiBaBO _ 3: RE (RE = Eu ~ (2 +)/ Tb ~ (3 +)/ Eu ~ (3 +)) phosphors are synthesized by high-temperature solid-phase conventional method. The emission spectrum, the excitation spectrum and the life decay curve of the sample were studied. In the atmosphere of strong reduction, the blue-green light of Eu ~ (2 +) was observed by the fluorescent powder of LiBaBO _ 3: Eu, and in the weakly-reduced atmosphere, the LiBaBO _ 3: Eu fluorescent powder. The coexistence of Eu ~ (2 +) and Eu ~ (3 +) ions will be observed. In addition, when the LiBaBO _ 3: Eu, Tb sample is sintered in the air, the phenomenon of the transfer of the Tb ~ (3 +) to the Eu ~ (3 +) is observed. The Eu ~ (2 +) ion, Eu ~ (3 +) ion and Tb ~ (3 +) ion co-exist in the condition of weak reduction, and the energy transfer of Eu ~ (2 +)-Tb ~ (3 +)-Eu ~ (3 +) ion occurs, and the color of the sample is obtained. It is also adjustable from blue to red. In other words, in the LiBaBO _ 3 matrix, the Tb ~ (3 +) ion can be used as a bridge for energy transfer to connect the Eu ~ (2 +) ion and the Eu ~ (3 +) ion, and finally the fluorescent powder with adjustable color is obtained. The results show that the Tb ~ (3 +) ions can be used as the storage energy of the Eu ~ (3 +) ions, and the LiBaBO _ 3 can be used as the potential matrix of the adjustable color of the LED. (2) A series of single-phase LiBaBO3: Ce ~ (3 +), AR (R = Eu ~ (2 +), Mn ~ (2 +), Dy ~ (3 +), Sm ~ (3 +), Tb ~ (3 +), and LiBaBO _ 3: Tb ~ (3 +), BE (E = Mn ~ (2 +), Dy ~ (3 +) and Sm ~ (3 +)) were synthesized by the high-temperature solid-phase method. It is found that the Ce ~ (3 +) ions can be combined with the co-doped Eu ~ (2 +)/ Mn ~ (2 +)/ Dy ~ (3 +)/ Sm ~ (3 +)/ Sm ~ (3 +)/ Tb ~ (3 +) ion in LiBaBO _ 3 matrix, and the energy is transferred to these ions by the interaction of the dipole-dipole. In addition, in the LiBaBO _ 3 matrix, when Tb ~ (3 +) ions are blended with other ions, the co-doped ions will affect the excitation spectrum of Tb ~ (3 +) ions. Finally, a series of color-tunable fluorescent powder is obtained by measuring the color coordinates of the sample. The results show that the LiBaBO _ 3 matrix has potential application value in the development of LED adjustable color. (3) A series of phosphors of Ce ~ (3 +)/ Tb ~ (3 +)/ Sm ~ (3 +)-doped Ba _ 2B _ 2O _ 5 matrix were prepared by high-temperature solid-phase method. When these three ions are individually doped in this matrix, blue, green, and red light-emitting colors are shown, respectively. When any two of these ions are co-doped in the Ba _ 2B _ 2O _ 5 matrix, the Ce ~ (3 +) ions can transfer energy to the Tb ~ (3 +) ions, and the same Tb ~ (3 +) ions can also transfer energy to the Sm ~ (3 +) ions. However, when the Ce ~ (3 +) and Sm ~ (3 +) ions are co-doped in the Ba _ 2B _ 2O _ 5 matrix, the Ce ~ (3 +) ions do not transfer the energy to the Sm ~ (3 +) ions. When the three ions are simultaneously doped in the Ba _ 2B _ 2O _ 5 matrix, the Tb ~ (3 +) ions can be used as the bridge for energy transfer to connect the Ce ~ (3 +) and Sm ~ (3 +) ions. In other words, in the Ba _ 2B _ 2O _ 5 matrix, the effect of the energy transfer between the three ions is realized by the bridge action of the Tb ~ (3 +) ions, and the white fluorescent powder is finally obtained. The experimental results show that the white phosphor doped with Ba _ 2B _ 2O _ 5: Ce, Tb and Sm has the potential to be applied to the white LED. (4) On the basis of Ba _ 2B _ 2O _ 5: Ce phosphor, Ba was replaced with Sr/ Ca/ Mg/ Zn, and a series of phosphors were obtained by using the traditional method of high-temperature solid phase, and the luminescent properties of the four kinds of phosphors were studied. Through a detailed analysis of the emission spectrum and the excitation spectrum, it is found that the best excitation of the series of cations to replace the fluorescent powder is located in the vicinity of 360 nm, and as the Ba ions are replaced by the four small radiuses, the emission spectrum is red shifted and then the blue shift gradually. In addition, the color coordinate position of the sample results in a small change in the color of the sample when the ions of the small radius are gradually replaced with the Ba ions. Thus, a method of fine-tuning the emission color of a sample is obtained by an experiment.
【學位授予單位】：河北大學
【學位級別】：碩士
【學位授予年份】：2017
【分類號】：O482.31
本文編號：2502727
[Abstract]:Based on the two kinds of borate LiBaBO _ 3 and Ba _ 2B _ 2O _ 5, different rare-earth ions, Eu ~ (2 +), Eu ~ (3 +), Tb ~ (3 +), Ce ~ (3 +), Sm ~ (3 +), Dy ~ (3 +), and transition metal Mn ~ (2 +), were synthesized by high-temperature solid-phase method. And the various properties of the synthesized fluorescent powder are studied in detail. The main contents of the study are as follows: (1) A series of LiBaBO _ 3: RE (RE = Eu ~ (2 +)/ Tb ~ (3 +)/ Eu ~ (3 +)) phosphors are synthesized by high-temperature solid-phase conventional method. The emission spectrum, the excitation spectrum and the life decay curve of the sample were studied. In the atmosphere of strong reduction, the blue-green light of Eu ~ (2 +) was observed by the fluorescent powder of LiBaBO _ 3: Eu, and in the weakly-reduced atmosphere, the LiBaBO _ 3: Eu fluorescent powder. The coexistence of Eu ~ (2 +) and Eu ~ (3 +) ions will be observed. In addition, when the LiBaBO _ 3: Eu, Tb sample is sintered in the air, the phenomenon of the transfer of the Tb ~ (3 +) to the Eu ~ (3 +) is observed. The Eu ~ (2 +) ion, Eu ~ (3 +) ion and Tb ~ (3 +) ion co-exist in the condition of weak reduction, and the energy transfer of Eu ~ (2 +)-Tb ~ (3 +)-Eu ~ (3 +) ion occurs, and the color of the sample is obtained. It is also adjustable from blue to red. In other words, in the LiBaBO _ 3 matrix, the Tb ~ (3 +) ion can be used as a bridge for energy transfer to connect the Eu ~ (2 +) ion and the Eu ~ (3 +) ion, and finally the fluorescent powder with adjustable color is obtained. The results show that the Tb ~ (3 +) ions can be used as the storage energy of the Eu ~ (3 +) ions, and the LiBaBO _ 3 can be used as the potential matrix of the adjustable color of the LED. (2) A series of single-phase LiBaBO3: Ce ~ (3 +), AR (R = Eu ~ (2 +), Mn ~ (2 +), Dy ~ (3 +), Sm ~ (3 +), Tb ~ (3 +), and LiBaBO _ 3: Tb ~ (3 +), BE (E = Mn ~ (2 +), Dy ~ (3 +) and Sm ~ (3 +)) were synthesized by the high-temperature solid-phase method. It is found that the Ce ~ (3 +) ions can be combined with the co-doped Eu ~ (2 +)/ Mn ~ (2 +)/ Dy ~ (3 +)/ Sm ~ (3 +)/ Sm ~ (3 +)/ Tb ~ (3 +) ion in LiBaBO _ 3 matrix, and the energy is transferred to these ions by the interaction of the dipole-dipole. In addition, in the LiBaBO _ 3 matrix, when Tb ~ (3 +) ions are blended with other ions, the co-doped ions will affect the excitation spectrum of Tb ~ (3 +) ions. Finally, a series of color-tunable fluorescent powder is obtained by measuring the color coordinates of the sample. The results show that the LiBaBO _ 3 matrix has potential application value in the development of LED adjustable color. (3) A series of phosphors of Ce ~ (3 +)/ Tb ~ (3 +)/ Sm ~ (3 +)-doped Ba _ 2B _ 2O _ 5 matrix were prepared by high-temperature solid-phase method. When these three ions are individually doped in this matrix, blue, green, and red light-emitting colors are shown, respectively. When any two of these ions are co-doped in the Ba _ 2B _ 2O _ 5 matrix, the Ce ~ (3 +) ions can transfer energy to the Tb ~ (3 +) ions, and the same Tb ~ (3 +) ions can also transfer energy to the Sm ~ (3 +) ions. However, when the Ce ~ (3 +) and Sm ~ (3 +) ions are co-doped in the Ba _ 2B _ 2O _ 5 matrix, the Ce ~ (3 +) ions do not transfer the energy to the Sm ~ (3 +) ions. When the three ions are simultaneously doped in the Ba _ 2B _ 2O _ 5 matrix, the Tb ~ (3 +) ions can be used as the bridge for energy transfer to connect the Ce ~ (3 +) and Sm ~ (3 +) ions. In other words, in the Ba _ 2B _ 2O _ 5 matrix, the effect of the energy transfer between the three ions is realized by the bridge action of the Tb ~ (3 +) ions, and the white fluorescent powder is finally obtained. The experimental results show that the white phosphor doped with Ba _ 2B _ 2O _ 5: Ce, Tb and Sm has the potential to be applied to the white LED. (4) On the basis of Ba _ 2B _ 2O _ 5: Ce phosphor, Ba was replaced with Sr/ Ca/ Mg/ Zn, and a series of phosphors were obtained by using the traditional method of high-temperature solid phase, and the luminescent properties of the four kinds of phosphors were studied. Through a detailed analysis of the emission spectrum and the excitation spectrum, it is found that the best excitation of the series of cations to replace the fluorescent powder is located in the vicinity of 360 nm, and as the Ba ions are replaced by the four small radiuses, the emission spectrum is red shifted and then the blue shift gradually. In addition, the color coordinate position of the sample results in a small change in the color of the sample when the ions of the small radius are gradually replaced with the Ba ions. Thus, a method of fine-tuning the emission color of a sample is obtained by an experiment.
【學位授予單位】：河北大學
【學位級別】：碩士
【學位授予年份】：2017
【分類號】：O482.31
【參考文獻】
相關期刊論文 前1條
1 張艷芳;李嵐;張曉松;奚群;;Temperature effects on photoluminescence of YAG:Ce~(3+) phosphor and performance in white light-emitting diodes[J];Journal of Rare Earths;2008年03期
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