Eu~2+、Ce~3+掺杂CaSi_2O_2N_2荧光粉的制备工艺和荧光性能研究
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摘要
本论文研究了CaSi_2O_2N_2:Eu~(2+)的制备工艺和Ca_(1-x)Eu_xSi_2O_-δN2+2/3δ(δ=0、1)荧光粉的荧光性能,对CaSi_2O_2N_2:Eu~(2+)的红移现象进行了深入探讨;采用HF酸处理对CaSi_2O_2N_2:Eu~(2+)微观形貌和荧光性能进行了改进;合成了CaSi_2O_2N_2:(Eu~(2+)/Ce~(3+))荧光粉,研究了其荧光性能和Ce~(3+)→Eu~(2+)的能量传递。
实验结果和计算分析表明:在1200°C -1500°C下均能合成CaSi_2O_2N_2:Eu~(2+) (δ=0)荧光材料,保温时间长短(1h-12h)对所形成物相结构影响很小,而对荧光发射强度的影响则很明显,这与高温下Eu_2O_3的还原速度和固溶进程有关;随着Eu~(2+)掺杂浓度的提高,CaSi_2O_2N_2:Eu~(2+)荧光发射光谱发射了红移现象和浓度猝灭效应,这是Eu~(2+)之间以偶极子相互作用的方式发生了能量传递造成的;在紫外-可见光(380-450nm)激发下,CaSi_2O_2N_2:Eu~(2+)发射出黄绿色光,波长峰值为530-550nm。1400°C保温6h,Eu~(2+)离子掺杂浓度为0.02的荧光材料能够与GaN/InGaN蓝光LED (450nm)配合得到2-pcLED;N/O比提高CaSi2ON8/3(δ=1),荧光材料的激发-发射光谱变宽,这是由于晶格中Eu~(2+)周围的晶体场强度增强造成的;经不同浓度HF酸处理,CaSi_2O_2N_2:Eu~(2+)的微观形貌发生改变,发射光谱均向长波方向移动;发射强度的改变与HF浓度有关,采用4%HF处理可以提高发射强度达一倍。
Ca1-x-2yEuxCeyLiySi2O2N2荧光材料被330nm紫外光激发,发射光谱表现为Ce~(3+)和Eu~(2+)两个发射峰,发射波长峰值分别位于～400nm和～550nm;x=0.02时,随着Ce~(3+)掺杂浓度提高,Eu~(2+)发射峰强度增加;y=0.01时,随着Eu~(2+)掺杂浓度x的增加,Ce~(3+)发射峰强度减弱这是Ce~(3+)→Eu~(2+)的能量传递造成的;Ca1-xEuxCe0.01Li0.01Si2O2N2荧光粉在紫外光激发下,发射出白光,颜色坐标为(0.167,0.05)~(0.349,0.521)。在单一晶格中实现白光发射,并且具有热和化学稳定性,是可以用于白光LED的荧光材料。
A series of CaSi_2O_2N_2:Eu~(2+) powders have been synthesized through solid-state reaction method under N2-H2 atmosphere. The formation and chemical reaction process was deduced from XRD patterns and PL spectrums of the powders. The crystal structure and fluorescence properties of Ca_(1-x)Eu_xSi_2O_-δN2+2/3δhave been systematically investigated (x=0, 0.005, 0.01, 0.02, 0.04, 0.05, 0.08, 0.1, 0.2;δ=0, 1). Red-shift and concentration quenching have been deeply discussed. HF treatments have been carried out to improve the microstructure and PL properties of the phosphors.(Eu~(2+), Ce~(3+)) co-doped CaSi_2O_2N_2 phosphors have also been prepared, and white light is obtained under UV excitation (330nm) due to Ce~(3+)→Eu~(2+) energy transfer mechanism.
The experiment results and analysis shows that: single phase CaSi_2O_2N_2:Eu~(2+) (δ=0) powders can be formed during 1200°C to 1500°C, the holding time (1h to 12h) of the above reaction temperatures contribute little to the crystal phase while influence the luminescence properties evidently; High N/O (δ=1) may broaden the excitation spectrum band due to strengthen of the crystal field strength around the Eu~(2+) in the phosphor lattice. As increasing the Eu~(2+) content, the emission spectrum of the phosphor show red-shift and concentration quenching (x=0.02) which due to the interaction between different Eu~(2+) diploes. CaSi_2O_2N_2:Eu~(2+) shows single broad band emission under UV-NUV excitation, centering at 530-550nm. HF treatment process could purify the phase and microstructure, improve the photoluminescence, increase the emission intensity, and the emission spectras change to longer wavelength band.
Introducing of Ce~(3+) caused increase of emission intensity of Eu~(2+), while increasing Eu~(2+) concentration the emission intensity of Ce~(3+) decreases due to energy migration over Eu~(2+) ions in the lattice. Resonance-type energy transfers from Ce~(3+) to Eu~(2+) were discovered by directly overlapping the Ce~(3+) emission spectra and the excitation spectra of Eu~(2+).The mechanism of non-radiative energy transfer from Ce~(3+) to Eu~(2+) is found to be electric dipole-dipole interaction. The CIE chromaticity coordinate of (Eu~(2+), Ce~(3+)) co-doped CaSi_2O_2N_2 phosphors vary form (0.167, 0.05) to (0.349, 0.521). Optimization of Eu~(2+) concentration was carried out to produce white light in the prepared Ca0.98-xEuxCe0.01Li0.01Si2O2N2.According to the principle of energy transfer, we demonstrated CaSi_2O_2N_2:Ce~(3+)/Eu~(2+) with blue and yellow emission bands exhibited a great potential as a phosphor for NUV-blue light-emitting diodes.
实验结果和计算分析表明:在1200°C -1500°C下均能合成CaSi_2O_2N_2:Eu~(2+) (δ=0)荧光材料,保温时间长短(1h-12h)对所形成物相结构影响很小,而对荧光发射强度的影响则很明显,这与高温下Eu_2O_3的还原速度和固溶进程有关;随着Eu~(2+)掺杂浓度的提高,CaSi_2O_2N_2:Eu~(2+)荧光发射光谱发射了红移现象和浓度猝灭效应,这是Eu~(2+)之间以偶极子相互作用的方式发生了能量传递造成的;在紫外-可见光(380-450nm)激发下,CaSi_2O_2N_2:Eu~(2+)发射出黄绿色光,波长峰值为530-550nm。1400°C保温6h,Eu~(2+)离子掺杂浓度为0.02的荧光材料能够与GaN/InGaN蓝光LED (450nm)配合得到2-pcLED;N/O比提高CaSi2ON8/3(δ=1),荧光材料的激发-发射光谱变宽,这是由于晶格中Eu~(2+)周围的晶体场强度增强造成的;经不同浓度HF酸处理,CaSi_2O_2N_2:Eu~(2+)的微观形貌发生改变,发射光谱均向长波方向移动;发射强度的改变与HF浓度有关,采用4%HF处理可以提高发射强度达一倍。
Ca1-x-2yEuxCeyLiySi2O2N2荧光材料被330nm紫外光激发,发射光谱表现为Ce~(3+)和Eu~(2+)两个发射峰,发射波长峰值分别位于～400nm和～550nm;x=0.02时,随着Ce~(3+)掺杂浓度提高,Eu~(2+)发射峰强度增加;y=0.01时,随着Eu~(2+)掺杂浓度x的增加,Ce~(3+)发射峰强度减弱这是Ce~(3+)→Eu~(2+)的能量传递造成的;Ca1-xEuxCe0.01Li0.01Si2O2N2荧光粉在紫外光激发下,发射出白光,颜色坐标为(0.167,0.05)~(0.349,0.521)。在单一晶格中实现白光发射,并且具有热和化学稳定性,是可以用于白光LED的荧光材料。
A series of CaSi_2O_2N_2:Eu~(2+) powders have been synthesized through solid-state reaction method under N2-H2 atmosphere. The formation and chemical reaction process was deduced from XRD patterns and PL spectrums of the powders. The crystal structure and fluorescence properties of Ca_(1-x)Eu_xSi_2O_-δN2+2/3δhave been systematically investigated (x=0, 0.005, 0.01, 0.02, 0.04, 0.05, 0.08, 0.1, 0.2;δ=0, 1). Red-shift and concentration quenching have been deeply discussed. HF treatments have been carried out to improve the microstructure and PL properties of the phosphors.(Eu~(2+), Ce~(3+)) co-doped CaSi_2O_2N_2 phosphors have also been prepared, and white light is obtained under UV excitation (330nm) due to Ce~(3+)→Eu~(2+) energy transfer mechanism.
The experiment results and analysis shows that: single phase CaSi_2O_2N_2:Eu~(2+) (δ=0) powders can be formed during 1200°C to 1500°C, the holding time (1h to 12h) of the above reaction temperatures contribute little to the crystal phase while influence the luminescence properties evidently; High N/O (δ=1) may broaden the excitation spectrum band due to strengthen of the crystal field strength around the Eu~(2+) in the phosphor lattice. As increasing the Eu~(2+) content, the emission spectrum of the phosphor show red-shift and concentration quenching (x=0.02) which due to the interaction between different Eu~(2+) diploes. CaSi_2O_2N_2:Eu~(2+) shows single broad band emission under UV-NUV excitation, centering at 530-550nm. HF treatment process could purify the phase and microstructure, improve the photoluminescence, increase the emission intensity, and the emission spectras change to longer wavelength band.
Introducing of Ce~(3+) caused increase of emission intensity of Eu~(2+), while increasing Eu~(2+) concentration the emission intensity of Ce~(3+) decreases due to energy migration over Eu~(2+) ions in the lattice. Resonance-type energy transfers from Ce~(3+) to Eu~(2+) were discovered by directly overlapping the Ce~(3+) emission spectra and the excitation spectra of Eu~(2+).The mechanism of non-radiative energy transfer from Ce~(3+) to Eu~(2+) is found to be electric dipole-dipole interaction. The CIE chromaticity coordinate of (Eu~(2+), Ce~(3+)) co-doped CaSi_2O_2N_2 phosphors vary form (0.167, 0.05) to (0.349, 0.521). Optimization of Eu~(2+) concentration was carried out to produce white light in the prepared Ca0.98-xEuxCe0.01Li0.01Si2O2N2.According to the principle of energy transfer, we demonstrated CaSi_2O_2N_2:Ce~(3+)/Eu~(2+) with blue and yellow emission bands exhibited a great potential as a phosphor for NUV-blue light-emitting diodes.
引文
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