Li~+,Zn~(2+),Mg~(2+)掺杂Lu_2O_3∶Er~(3+)荧光粉的制备及发光特性
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摘要
用微波高温固相法合成了Er~(3+)单掺Lu_2O_3,Li~+与Er~(3+)共掺Lu_2O_3及Li~+,Zn~(2+),Mg~(2+)掺杂Lu_2O_3∶Er~(3+)的荧光粉。实验表明金属离子Li~+、Zn~(2+)、Mg~(2+)、Er~(3+)掺杂Lu_2O_3,不影响Lu_2O_3的立方晶相。扫描电子显微镜测量表明,Li~+掺杂可以有效改善粉体的分散性和形貌,Li~+,Zn~(2+),Mg~(2+)共掺杂获得的粉体颗粒分布更加均匀,粒径范围为80～100 nm。379 nm激发下,Li~+与Er~(3+)共掺样品发光较单掺Er~(3+)样品在565 nm处的发光增强了4.5倍,而Li~+、Zn~(2+)、Mg~(2+)与Er~(3+)共掺样品较其发光增强5.3倍。980 nm激发下,Li~+与Er~(3+)共掺样品,Li~+、Zn~(2+)、Mg~(2+)与Er~(3+)共掺样品的发光分别比单掺Er~(3+)样品在565 nm处发光增强23倍与39倍,在662 nm处发光强度分别增强20倍与43倍。379 nm激发下,较单掺Er~(3+)的样品,掺杂Li~+的样品和Li~+,Zn~(2+),Mg~(2+)和Er~(3+)共掺的样品荧光寿命均有所增加,而Zn~(2+)、Er~(3+)共掺及Mg~(2+)、Er~(3+)共掺样品的荧光寿命则有所缩短。
Li~+,Zn~(2+),Mg~(2+),Er~(3+)doped Lu_2O_3 phosphors were synthesized using the microwave heating hightemperature solid state method.The experimental results indicate that doping with Li~+,Zn~(2+),Mg~(2+)and Er~(3+)will not affect the cubic phase of Lu_2O_3.SEM measurements show that Li~+doping can effectively improve the dispersibility and morphology of the sample powder,and the powder particle size distribution obtained by the co-doping of Li~+,Zn~(2+)and Mg~(2+)are more uniform with a particle size of 80-100 nm.The excitation spectra,emission spectra and the fluorescence lifetime of the samples were detected and analyzed using a fluorescence spectrophotometer.The results showed that under 379 nm excitation,the luminescence intensities of samples doped with 5%Li~+and 2%Er~(3+),and that of samples doped with 5%Li~+,2.5%Zn~(2+),2.5%Mg~(2+)and 2%Er~(3+)increased by 4.5 and 5.3 times than that of the sample only doped with Er~(3+)ions at 565 nm.Under 980 nm excitation,the up-conversion luminescence intensities of samples doped with 5% Li~+ and 2% Er~(3+),and that of samples doped with 5% Li~+,2.5% Zn~(2+),2.5% Mg~(2+) and 2% Er~(3+)increased by 23 and 39 times than that of samples doped only with Er~(3+)ions at 565 nm.This increased by 20 and 43 times at 662 nm.Under 379 nm excitation,the lifetime of the samples doped with Li~+was longer than that without Li~+.The lifetime of the samples co-doped with Li~+,Zn~(2+),Mg~(2+) and Er~(3+) increased,while the lifetime of the samples co-doping of Zn~(2+),Er~(3+) and Mg~(2+),Er~(3+) decreased.
Li~+,Zn~(2+),Mg~(2+),Er~(3+)doped Lu_2O_3 phosphors were synthesized using the microwave heating hightemperature solid state method.The experimental results indicate that doping with Li~+,Zn~(2+),Mg~(2+)and Er~(3+)will not affect the cubic phase of Lu_2O_3.SEM measurements show that Li~+doping can effectively improve the dispersibility and morphology of the sample powder,and the powder particle size distribution obtained by the co-doping of Li~+,Zn~(2+)and Mg~(2+)are more uniform with a particle size of 80-100 nm.The excitation spectra,emission spectra and the fluorescence lifetime of the samples were detected and analyzed using a fluorescence spectrophotometer.The results showed that under 379 nm excitation,the luminescence intensities of samples doped with 5%Li~+and 2%Er~(3+),and that of samples doped with 5%Li~+,2.5%Zn~(2+),2.5%Mg~(2+)and 2%Er~(3+)increased by 4.5 and 5.3 times than that of the sample only doped with Er~(3+)ions at 565 nm.Under 980 nm excitation,the up-conversion luminescence intensities of samples doped with 5% Li~+ and 2% Er~(3+),and that of samples doped with 5% Li~+,2.5% Zn~(2+),2.5% Mg~(2+) and 2% Er~(3+)increased by 23 and 39 times than that of samples doped only with Er~(3+)ions at 565 nm.This increased by 20 and 43 times at 662 nm.Under 379 nm excitation,the lifetime of the samples doped with Li~+was longer than that without Li~+.The lifetime of the samples co-doped with Li~+,Zn~(2+),Mg~(2+) and Er~(3+) increased,while the lifetime of the samples co-doping of Zn~(2+),Er~(3+) and Mg~(2+),Er~(3+) decreased.
引文
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[2]庹娟,王林香,叶颖,等.金属离子Li+,Na+,K+,Ca2+,Ba2+掺杂Lu2O3∶Pr3+荧光粉的制备及发光特性研究[J].发光学报,2018,39(3):307-314.TUO J,WANG L X,YE Y,et al..Preparation and luminescence properties of Lu2O3∶Pr3+phosphors codoped with Li+,Na+,K+,Ca2+,Ba2+ions[J].Chinese Journal of Luminescence,2018,39(3):307-314.(in Chinese)
[3]CHEN G Y,LIANG H J,LIU H C,et al..Anomalous power dependence of upconversion emissions in Gd2O3∶Er3+nanocrystals[J].Journal of Applied Physics,2009,105:1-5.
[4]肖思国,阳效良,丁建文.Er3+,Er3+/Yb3+掺杂氟化镧超微材料的光谱特性与上转换发光[J].物理学报,2009,58(6):3812-3820.XIAO S G,YANG X L,DING J W.Luminescence properties and upconversion of Er3+doped and Er3+/Yb3+co-doped La F3particles[J].Acta Physica Sinica,2009,58(6):3812-3820.(in Chinese)
[5]王鹏贺.Er3+∶Lu2O3纳米粉体和透明陶瓷的制备及光谱性质研究[D].长春:长春理工大学,2011.WANG P H.Preparation and spectroscopic properties of Er3+∶Lu2O3nano powders and transparent ceramics[D].Changchun:Changchun University of Science and Technology,2011.(in Chinese)
[6]LI T,BEIL K,KRNKEL C,et al..Efficient high-power continuous wave Er∶Lu2O3laser at 2.85μm[J].Optics Letters,2012,37(13):2568-2570.
[7]刘禄.Er3+/Yb3+/Li+掺杂氧化物纳米晶上转换荧光机制及应用研究[D].哈尔滨:哈尔滨工业大学,2011.LIU L.Upconversion mechanisms of Er3+/Yb3+/Li+doped oxde nanocrystals and their applications[D].Harbin:Harbin Institute of Technology,2011.(in Chinese)
[8]徐赛.LD泵浦3微米Er固体激光器输出特性研究[D].哈尔滨:哈尔滨工业大学,2015.XU S.Studies on output performance of 3 micron band Er-doped solid state lasers pumped by LD[D].Harbin:Harbin Institute of Technology,2015.(in Chinese)
[9]李玮楠,邹快盛,陆敏,等.掺Er3+硅酸盐玻璃上转换发光特性研究[J].无机材料学报,2007,22(1):30-34.LI W N,ZOU K SH,LU M,et al..Properties of up-conversion emission of Er3+doped silicate glasses[J].Journal of Inorganic Materials,2007,22(1):30-34.(in Chinese)
[10]李艳平.稀土激活的Lu BO3、Lu2O3纳米材料的制备与发光性质[D].长春:长春光学精密机械与物理研究所,2010.LI Y P.Preparation and luminescence properties of Lu BO3and Lu2O3nanomaterials activated by rare earth ions[D].Changchun:Changchun Institute of Optics,Fine Mechanics and Physics,2010.(in Chinese)
[11]徐斌,周勇强,王荷,等.Er3+掺杂钇稳定氧化锆的上转换发光[J].光谱学与光谱分析,2014,34(12):3214-3217.XU B,ZHOU Y Q,WANG H,et al..Upconversion luminescence of Er3+doped Yttrium-stabilized Zirconia powders[J].Spectroscopy and Spectral Analysis,2014,34(12):3214-3217.(in Chinese)
[12]尹玲珍.Yb3+、Er3+/Ho3+共掺杂的Lu2O3、KSc F4上转换纳米晶的可控合成及发光性质研究[D].武汉:湖南师范大学,2015.YIN L ZH.Controllable synthesis and luminescent properties of Yb3+,Er3+/Ho3+codoped Lu2O3、KSc F4up conversion nano-materials[D].Wuhan:Hunan Normal University,2015.(in Chinese)
[13]刘冰洁,顾牡,刘小林,等.Li+,Zn2+共掺杂对Gd2O3;Eu3+纳米粉结构和发光性能的影响[J].中国稀土学报,2007,25(2):162-166.LIU B J,GU M,LIU X L,et al..Effect of Li+and Zn2+co-doping on luminescent properties of Gd2O3∶Eu3+nanoparticles[J].Journal of the Chinese Rare Earth Society,2007,25(2):162-166.(in Chinese)
[14]刘吉地,王育华.Mg2+掺杂Zn2Si O4∶Mn2+的溶胶-凝胶法合成及真空紫外发光特性研究[J].物理学报,2010,59(5):3558-3563.LIU J D,WANG Y H.Synthesis and luminescent properties of Mg2+doped Zn2Si O4∶Mn2+phosphor under VUV excitation[J].Acta Physica Sinica,2010,59(5):3558-3563.(in Chinese)
[15]杨英,陈永杰,肖林久,等.Sr3B2O6∶Eu3+,Li+荧光粉的合成与发光性能[J].发光学报,2014,35(3):317-321.YANG Y,CHEN Y J,XIAO L J,et al..Synthesis and luminescent properties of Sr3B2O6∶Eu3+,Li+phosphor[J].Chinese Journal of Luminescence,2014,35(3):317-321.(in Chinese).
[16]庹娟,王林香,李敏.Li+、Na+和Eu3+共掺Lu2O3的制备及发光特性研究[J].发光学报,2016,37(1):28-32.TUO J,WANG L X,LI M.Preparation and luminescence properties of Li+,Na+and Eu3+co-doped Lu2O3[J].Chinese Journal of Luminescence,2016,37(1):28-32.(in Chinese)
[17]SERIVALSATIT K,WASANAPIARNPONG T,KUCERA C,et al..Synthesis of Er-doped Lu2O3nanoparticles and transparent ceramics[J].Optical Materials,2013,35(7):1426-1430.
[18]王林香.合成条件对(Eu0.045Li3xLuy)2O3纳米晶发光性能影响[J].光学学报,2016,36(3):35-42.WANG L X.Luminescent properties of(Eu0.045Li3xLuy)2O3nanocrystals by precipitation[J].Acta Optica Sinica,2016,36(3):35-42.(in Chinese)
[19]LI W,LEE J.Microwave-assisted sol-gel synthesis and photo-luminescence characterization of La PO4∶Eu3+,Li+nanophosphors[J].Journal of Physical Chemistry C,2008,112(31):11679-11684.
[20]郑贤火.非稀土金属离子掺杂对氧化钇粉末荧光性能的影响[D].杭州:浙江理工大学,2016.ZHEN X H.Effects of non-rare-earth metal ions doping on the fluorescent properties of yttrium oxide powder[D].Hangzhou:Zhejiang Sci-Technology University,2016.(in Chinese)
[21]STUDENIKIN S A,NGOLEGO N,COCIVERA M.Fabrication of green and orange photoluminescent,undoped Zn O films using spray pyrolysis[J].J.Appl.Phys.,1998,84:2287.
[22]徐会兵,庄卫东,胡运生,等.碱金属离子掺杂对(Y,Gd)BO3∶Tb绿色荧光粉性能的影响[C].2010年全国冶金物理化学学术会议论文集,2010:268-272.XU H B,ZHUANG W D,HU Y SH,et al..Influence of alkaline metal ions doping on properties of(Y,Gd)BO3∶Tb[C].Proceedings of the national conference on metallurgy and physical chemistry in 2010,2010,268-272.(in Chinese)
[23]王林香,李敏,庹娟.沉淀法制备(Eu0.045Li3xNa3yGdz/Luw)2O3纳米晶及发光性能研究[J].人工晶体学报,2015,44(12):3671-3675.WANG L X,LI M,TUO J.Luminescent properties of(Eu0.045Li3xNa3yGdz/Luw)2O3nanocrystals by precipitation[J].Journal of Synthetic Cryatals,2015,44(12):3671-3675.(in Chinese)
[24]李小女.Er3+,Na+,Ca F2透明陶瓷的制备及性能研究[D].武汉:武汉理工大学,2012.LI X N.Study on preparation and properties of Er3+,Na+codoping Ca F2transparent ceramics[D].Wuhan:Wuhan University of Technology,2012.(in Chinese)
[25]BACHIR S,AZUMA K,KOSSANYI J,et al..Photoluminescence of polycrystalline zinc oxide co-activated with trivalent rare earth ions and lithium.Insertion of rare-earth ions into zinc oxide[J].J.Lumin.,1997,75:35-49.
[26]WANG J,ZHANG H R,LIU Y L,et al..Insights into luminescence quenching and detecting trap distribution in Ba2Si5N8∶Eu2+phosphor with comprehensive considerations of temperature dependent luminescence behaviors[J].Journal of Materials Chemistry C,2015,3(37):9572-9579.
[27]XIA Z G,MIAO S H,CHEN M Y,et al..Structure,crystal lographic sites and tunable luminescence properties of Eu2+and Ce3+/Li+activated Ca1.65Sr0.35Si O4phosphors[J].Inorganic Chemistry,2015,54(16):7684-7691.