钛酸钙镨红色长余辉发光粉体和薄膜的制备及性能研究
|
摘要
长余辉发光材料是一种关闭光源后仍能持续长时间发光的新型功能材料,被广泛应用于紧急照明、军事、工艺美术、光信息存储、成像显示和辐射探测等领域,其形态由粉末扩展到薄膜、玻璃、陶瓷等。但是作为三基色之一的红色长余辉发光材料的发光性能还不能达到实际应用的要求,在一定程度上抑制了长余辉材料的应用。所以研发新型红色长余辉发光材料成为当前急需解决的问题。CaTiO3:Pr3+红色长余辉发光材料具有良好的稳定性及其色坐标值(x=0.68,y=0.31)与NTSC的理想红色坐标(x=0.67,y=0.33)非常接近,引起了人们广泛的关注。本文旨在通过新的溶胶凝胶燃烧法的工艺制备该类红色长余辉发光材料,以期研究开发一种廉价、无污染的高效节能型红色长余辉发光材料。
本工作在前人实验研究CaTiO3:Pr3+红色长余辉发光材料的基础上,研究发现了能够利用溶胶凝胶燃烧法制备CaTio3：Pr3+红色长余辉发光材料。这一发现克服了用传统的高温固相法制备发光材料煅烧温度高、制备的样品颗粒尺寸大的缺点,并且避免了溶胶凝胶法制备发光材料时湿凝胶制备干凝胶的过程,缩短了生产周期,达到了节时、节能的效果。
本文首次采用溶胶凝胶燃烧法以CaTiO3为基质、硝酸锌为助溶剂、碳酸钠为电荷补偿剂成功制备了Ca0.8Zn0.2TiO3:Pr3+,Na+纳米红色长余辉发光材料。利用XRD、SEM、荧光分光光度计、热释光谱仪和照度计研究了Pr3+含量、烧结温度、恒温时间、升温速率对样品物相、形貌以及发光性能的影响。结果显示,样品的激发峰为328 nm,发射峰为613 nm,余辉时间最长达10Omin(≥mcd/m2)经过对比实验,确定了制备Ca0.8Zn0.2TiO3:Pr3+,Na+纳米红色长余辉发光材料的最佳条件：名义组分Ca0.796Zn0.2TiO3:0.002Pr3+0.002Na+、煅烧温度800℃、恒温时间3h、升温速率5～7℃/min。
近年来长余辉发光薄膜被提出可应用于场发射显示器件,本文将溶胶凝胶燃烧法制备Ca0.8Zn0.2TiO3:Pr3+,Na+的最佳参数应用于制备Ca0.8Zn0.2TiO3:Pr3+,Na+长余辉发光薄膜。利用XRD、SEM、荧光分光光度计和照度计研究了烧结温度、溶胶浓度、提拉速度、薄膜层数对薄膜物相、形貌以及发光性能的影响。结果显示,样品的激发峰为328 nm,发射峰为614 nm,较粉体发生了1 nm的红移,余辉时间最长达130s(≥mcd/m2)。经过对比实验,确定了制备Ca0.8Zn0.2TiO3:Pr3+,Na+纳米红色长余辉发光薄膜的最佳条件：煅烧温度850℃、溶胶浓度0.25～0.3mol/L、提拉速度7.36～10.36cm/min(10～13V)、薄膜层数8层。
The long afterglow phosphor is a new functional material that can illuminate for a long time after the lamp-house is closed. This material has been applied in lots of domains such as emergent illumination, military affairs, industrial arts, optical data storage, imaging showed and radiation detection etc. The type was expanded from powder to film, glass, ceramics, etc. But as one of primary colors, the red long persistent materials cannot achieve actual application requirements yet. The application is restrained by the deficiency of the red long afterglow phosphor. So research and development of new red long afterglow phosphorescent materials become the urgent problems to be resolved. The red long afterglow phosphor CaTiO3:Pr3+ has good stability and high quality red emission with chromaticity coordinates positioned at x=0.680 and y=0.311, which are very close to those of the NTSC ideal red emission (x=0.67, y=0.33). In this paper, calcium titanate phosphors were prepared by a new method of sol-gel-combustion process in order to research and develop a sort of cheap, environmental friendly and high-efficient red long afterglow phosphors materials.
This work was expanded on the basis of predecessors's experimental result on CaTiO3:Pr3+ red long-glow phosphor. We found that the red long afterglow luminescent nanomaterial Ca0.8Zn0.2TiO3:Pr3+,Na+ can be synthesised by sol-gel combustion method.This discovery overcomes high calcining temperature and big particle size when CaTiO3:Pr3+ phosphor was synthesised by traditional high temperature solid phase reaction, and avoids process from wet gel to dry gel. This method shorten the production cycle,and save the time and energy.
The red long afterglow luminescent nanomaterial Ca01.8Zn0.2TiO3:Pr3+,Na+ was first synthesised by sol-gel combustion method with CaTiO3 for matrix, zinc nitrate for cosolvent, sodium carbonate for charge compensation agent. Effects of Pr3+ content, calcination temperatures,constant temperature time and heating rate on the crystal characteristics, surface morphology and luminescent properties of the samples were investigated using XRD, SEM, fluorescence spectrophotometer and thermally stimulated spectrometer. Results indicate: Sample excitation peak centered at 328nm and appears a single peak centered at 613nm. The longest afterglow time is 10min(≥1mcd/m2). Through contrast test, the optimum condition of manufacturing red long afterglow luminescent nanomaterial Ca0.8Zn0.2TiO3:Pr3+,Na+ is determined:The nominal composition is Ca0.796Zn0.2TiO3:0.002Pr3+,0.002Na+;Calcination temperature is 800℃; Constant temperature time is 3h;Heating rate is 5～7℃/min.
In recent years long afterglow luminescent film which can be applied to field emission display device was proposed. Long afterglow luminescent Ca0.8Zn0.2TiO3:Pr3+ was synthesized in this paper, on the basis of optimum condition of synthesizing long afterglow luminescent film Ca0.8Zn0.2TiO3:Pr3+,Na+ by sol-gel combustion method. Effects of calcination temperatures, sol concentration, tiras speed and the number of film layer on the crystal characteristics, surface morphology and luminescent properties of the samples were investigated using XRD, SEM, fluorescence spectrophotometer and thermally stimulated spectrometer. Results indicate that sample excitation peak centered at 328 nm, emission peak at 614 nm, 1nm redshift is happened compared to previous powder, and the longest of afterglow time reach 130s. Through contrast experimental, we find the optimum condition of synthesizing Ca0.8Zn0.2TiO3:Pr3+,Na+ long afterglow luminescent film.Calcination temperatures is 850℃,sol concentration is 0.25～0.3mol/L, tiras speed is 7.36～10.36cm/min(10～13V),and the number of film layer is 8.
本工作在前人实验研究CaTiO3:Pr3+红色长余辉发光材料的基础上,研究发现了能够利用溶胶凝胶燃烧法制备CaTio3：Pr3+红色长余辉发光材料。这一发现克服了用传统的高温固相法制备发光材料煅烧温度高、制备的样品颗粒尺寸大的缺点,并且避免了溶胶凝胶法制备发光材料时湿凝胶制备干凝胶的过程,缩短了生产周期,达到了节时、节能的效果。
本文首次采用溶胶凝胶燃烧法以CaTiO3为基质、硝酸锌为助溶剂、碳酸钠为电荷补偿剂成功制备了Ca0.8Zn0.2TiO3:Pr3+,Na+纳米红色长余辉发光材料。利用XRD、SEM、荧光分光光度计、热释光谱仪和照度计研究了Pr3+含量、烧结温度、恒温时间、升温速率对样品物相、形貌以及发光性能的影响。结果显示,样品的激发峰为328 nm,发射峰为613 nm,余辉时间最长达10Omin(≥mcd/m2)经过对比实验,确定了制备Ca0.8Zn0.2TiO3:Pr3+,Na+纳米红色长余辉发光材料的最佳条件：名义组分Ca0.796Zn0.2TiO3:0.002Pr3+0.002Na+、煅烧温度800℃、恒温时间3h、升温速率5～7℃/min。
近年来长余辉发光薄膜被提出可应用于场发射显示器件,本文将溶胶凝胶燃烧法制备Ca0.8Zn0.2TiO3:Pr3+,Na+的最佳参数应用于制备Ca0.8Zn0.2TiO3:Pr3+,Na+长余辉发光薄膜。利用XRD、SEM、荧光分光光度计和照度计研究了烧结温度、溶胶浓度、提拉速度、薄膜层数对薄膜物相、形貌以及发光性能的影响。结果显示,样品的激发峰为328 nm,发射峰为614 nm,较粉体发生了1 nm的红移,余辉时间最长达130s(≥mcd/m2)。经过对比实验,确定了制备Ca0.8Zn0.2TiO3:Pr3+,Na+纳米红色长余辉发光薄膜的最佳条件：煅烧温度850℃、溶胶浓度0.25～0.3mol/L、提拉速度7.36～10.36cm/min(10～13V)、薄膜层数8层。
The long afterglow phosphor is a new functional material that can illuminate for a long time after the lamp-house is closed. This material has been applied in lots of domains such as emergent illumination, military affairs, industrial arts, optical data storage, imaging showed and radiation detection etc. The type was expanded from powder to film, glass, ceramics, etc. But as one of primary colors, the red long persistent materials cannot achieve actual application requirements yet. The application is restrained by the deficiency of the red long afterglow phosphor. So research and development of new red long afterglow phosphorescent materials become the urgent problems to be resolved. The red long afterglow phosphor CaTiO3:Pr3+ has good stability and high quality red emission with chromaticity coordinates positioned at x=0.680 and y=0.311, which are very close to those of the NTSC ideal red emission (x=0.67, y=0.33). In this paper, calcium titanate phosphors were prepared by a new method of sol-gel-combustion process in order to research and develop a sort of cheap, environmental friendly and high-efficient red long afterglow phosphors materials.
This work was expanded on the basis of predecessors's experimental result on CaTiO3:Pr3+ red long-glow phosphor. We found that the red long afterglow luminescent nanomaterial Ca0.8Zn0.2TiO3:Pr3+,Na+ can be synthesised by sol-gel combustion method.This discovery overcomes high calcining temperature and big particle size when CaTiO3:Pr3+ phosphor was synthesised by traditional high temperature solid phase reaction, and avoids process from wet gel to dry gel. This method shorten the production cycle,and save the time and energy.
The red long afterglow luminescent nanomaterial Ca01.8Zn0.2TiO3:Pr3+,Na+ was first synthesised by sol-gel combustion method with CaTiO3 for matrix, zinc nitrate for cosolvent, sodium carbonate for charge compensation agent. Effects of Pr3+ content, calcination temperatures,constant temperature time and heating rate on the crystal characteristics, surface morphology and luminescent properties of the samples were investigated using XRD, SEM, fluorescence spectrophotometer and thermally stimulated spectrometer. Results indicate: Sample excitation peak centered at 328nm and appears a single peak centered at 613nm. The longest afterglow time is 10min(≥1mcd/m2). Through contrast test, the optimum condition of manufacturing red long afterglow luminescent nanomaterial Ca0.8Zn0.2TiO3:Pr3+,Na+ is determined:The nominal composition is Ca0.796Zn0.2TiO3:0.002Pr3+,0.002Na+;Calcination temperature is 800℃; Constant temperature time is 3h;Heating rate is 5～7℃/min.
In recent years long afterglow luminescent film which can be applied to field emission display device was proposed. Long afterglow luminescent Ca0.8Zn0.2TiO3:Pr3+ was synthesized in this paper, on the basis of optimum condition of synthesizing long afterglow luminescent film Ca0.8Zn0.2TiO3:Pr3+,Na+ by sol-gel combustion method. Effects of calcination temperatures, sol concentration, tiras speed and the number of film layer on the crystal characteristics, surface morphology and luminescent properties of the samples were investigated using XRD, SEM, fluorescence spectrophotometer and thermally stimulated spectrometer. Results indicate that sample excitation peak centered at 328 nm, emission peak at 614 nm, 1nm redshift is happened compared to previous powder, and the longest of afterglow time reach 130s. Through contrast experimental, we find the optimum condition of synthesizing Ca0.8Zn0.2TiO3:Pr3+,Na+ long afterglow luminescent film.Calcination temperatures is 850℃,sol concentration is 0.25～0.3mol/L, tiras speed is 7.36～10.36cm/min(10～13V),and the number of film layer is 8.
引文
[1]徐叙瑢,苏勉曾.发光学与发光材料[M].北京：化学工业出版社,2004：112-113,604-605.
[2]Qiu J., Miura K., Inouye H., et al. Femtosecond laser induced three dimensional bright and long lasting phosphorescence inside calcium aluminosilicate glasses doped with rare earth ions[J]. Applied Physics Letters,1998,73:1763-1765.
[3]Kowatari M., Koyama D., Satoh Y., et al. The temperature dependence of luminescence from a long lasting phosphors exposed to ionizing radiation [J]. Nuclear Instruments and Methods in Physics Research A,2002,480:431-439.
[4]Sung Mook Chung, Sang hyuk Han, Kuk Hyun Song, et al. Luminescent properties of CaTiO3:Pr3+ thin-film phosphor deposited on ZnO/ITO/glass substrate[J]. Journal of Luminescence,2005,114:227-233.
[5]Sato K., Komuro S.,Morikawa T.,et al. Long afterglow characteristics of thin film phosphor fabricated by laser ablation[J].Journal of Crystal Growth,2005,275:137-141.
[6]Pinel Eric, Boutinaud Philippe, Bertrand Genevieve, et al. Preparation and characterization of luminescent films of Pr3+-doped CaTiO3 processed by sol-gel technique[J]. Journal of Alloys and Compounds,2004,374:202-206.
[7]杨志平,刘冲,郭智等.CaTiO3:Pr3+长余辉玻璃的制备与发光性能[J].发光学报,2005,26(4)：493-496.
[8]朱爱玲,廉世勋,李承志等.绿色长余辉发光玻璃的合成和性质[J].光谱实验室,2003,20(1)：23-27.
[9]Lin Yuanhua, Tang Zilong, Zhang Zhongtai, et al. Preparation and properties of photoluminescent rare earth doped SrO-MgO-B2O3-SiO2 glass[J]. Materials Science and Engineering:B,2001,86:79-82.
[10]Chang Chengkang, Mao Dali, Shen Jianfeng, et al. Preparation of long persistent SrO·2Al2O3 ceramics and their luminescent properties [J]. Journal of Alloys and Compounds,2003,348:224-230.
[11]Chang C.K., Jiang L., Mao D.L., et al. Photoluminescence of 4Sr0.7Al2O3 ceramics sintered with the aid of B2O3[J]. Ceramics International,2004,30:285-290.
[12]Jia Yi, Ye Ming, Jia Weiyi. Stress-induced mechanoluminescence in SrAl2O4:Eu2+,Dy3+[J]. Optical Materials,2006,28(9):974-979.
[13]Zhao Changliang, Chen Donghua, Yuan Yuhong, et al. Synthesis of Sr4Al14O25:Eu2+, Dy3+ phosphor nanometer powders by combustion processes and its optical properties[J]. Materials Science and Engineering:B,2006,133(3):200-204.
[14]薛红伟,崔彩娥,黄平等.烧结温度对蓝色长余辉材料Sr2Al6O11:Eu2+,Dy3+发光性能的影响[J].人工晶体学报,2009,38(6)：1384-1387.
[15]Jia Weiyi, Yuan Huabiao, Lu Lizhu, et al. Phosphorescent dynamics in SrAl2O4:Eu2+,Dy3+ single crystal fibers[J]. Journal of Luminescence,1998,76-77:424-428.
[16]Tang Jinfeng, Yu Xibin, Yang Liangzhun, et al. Preparation and Al3+ enhanced photoluminescence properties of CaTiO3:Pr3+[J].Materials Letters,2006,60:326-329.
[17]Zhang Juncheng, Wang Xusheng, Yao Xi. Enhancement of luminescence and afterglow in CaTiO3:Pr3+ by Zr substitution for Ti[J]. Journal of Alloys and Compounds,2010, 498:152-156.
[18]Wang Rong, Meng Jianxin. Hydrothermal preparation and characterization of long-afterglow phosphors CaTiO:Pr,Al [J]. Journal of the Chinese Rare Earth Society, 2009,27(3):349.
[19]Wang Xusheng, Xu Chaonan, Yamada Hiroshi. Enhancement of photoluminescence in CaTiO3:Pr3+ by Ba and Sr substitution for Ca [J].Jpn. J. Appl. Phys.2005,44:L912.
[20]张英兰,赵绪义,葛中久.Dy3+在Ca1-xSrxS:Eu2+,Er3+中的光致发光特性[J].吉林大学自然科学学报,1997,4：52-54.
[21]贾冬冬,姜联合,刘玉龙等.CaxSr1-xS:Bi,Tm,Cu和 CaS:Eu荧光材料的研究[J].发光学报,1998,19(4)：312-316.
[22]戴国瑞,郑燕,张英兰.非放射性红色发光材料的合成与发光[J].吉林大学学报(理学版),1993,1：97-100.
[23]袁曦明,许永胜,于江波等.红色长余辉发光材料CaS:Eu2+,Tm3+的制备研究[J].材料开发与应用,2002,17(3)：21-24.
[24]肖志国.硫化物长余辉发光材料及制造方法[P].中国专利：CN97111381,1997.
[25]Murazaki Y, Arak K, Ichinomiya K. A new long persistence red phosphor [J]. Japanese Rare Earth (in Japan),1999,35:41-45.
[26]李灿涛,袁剑辉,张万锴等.掺杂Gd3+对Y2O2S:Eu3+发光特性的影响[J].发光学报,1999,20(4)：316-319.
[27]宋春燕,雷炳富,刘应亮等.Eu3+在La2O2S中的长余辉发光[J].无机化学学报,2004,20(1)：89-93.
[28]宋春燕,王晓华,刘应亮等.新型橙红色长余辉发光材料Gd2O2S:Sm3+的合成[J].化学通报,2004,5：373-376.
[29]宋春燕,刘应亮,张静娴等.微波法合成橙红色长余辉磷光粉Gd2O2S:Sm3+[J].暨南大学学报(自然科学版),2003,24(5)：93-96.
[30]Wang Xiaoxin, Zhang Zhongtai, Tang Zilong, et al. Characterization and properties of a red and orange Y2O2S-based long afterglow phosphor [J]. Materials chemistry and physics,2003,80(1):1-5.
[31]Lei Bingfu, Liu Yingliang, Tang Gongben, et al. Spectra and long lasting properties of Sm3+ doped yttrium oxysulfide phosphor [J]. Materials chemistry and physics,2004, 87(1):227-232.
[32]杨志平,郭智,王文杰等.Y2O2S:Eu3+,Mg2+,Ti4+红色材料的制备和长余辉性能[J].发光学报,2004,25(2)：183-187.
[33]Wang Xiaojun, Jia Dongdong, Yen W.M. Mn2+activated green, yellow, and red long persistent phosphors [J]. Journal of Luminescence,2003, (102-103):34-37.
[34]Lei Bingfu, Liu Yingliang, Liu Jie, et al. Pink light emitting long lasting phosphorescence in Sm3+ doped CdSiO3 [J], Journal of Solid State Chemistry.2004,177(4-5):1333-1337.
[35]Lei Bingfu, Liu Yingliang, Ye Zeren, et al.Luminescence properties of CdSiO3：Mn2+ phosphor [J]. Journal of Luminescence,2004,109(3-4):215-219.
[36]Froelich H.C. Strontium Aluminate Phosphor [P], US Patent:2392814,1946.
[37]Palilla F.C., Luvine A.K., Tonikus M.R.. Fluoerscent Properties of alkaline earth aluminates of the type MAl2O4 activated by divalent europium [J]. Journal of The Electrochemical Society,1968,115(6):642-648.
[38]Pallavi Page, Rahul Ghildiyal, Murthy K.V.R.. Synthesis, characterization and luminescence of Sr2Al2O6 phosphor with trivalent rare earth dopant [J],Materials Research Bulletin,2006,41(10):1854-1860.
[39]Zhang Ping, Xu Mingxia. Zheng Zhentai, et al. Microwave synthesis and characterization of new red long afterglow phosphor Sr3Al2O6:Eu [J]. Transactions of Nonferrous Metals Society of China,2006,16:423-425.
[40]Pan Yuexiao, Herman H.-Y.Sung, Wu Hao, et al, Hydrothermally-mediated preparation and photoluminescent properties of Sr3Al2O6:Eu3+ phosphor [J]. Materials Research Bulletin,2006,41(2):225-231.
[41]Zhong Ruixia, Zhang Jiahua, Zhang Xia,et al. Energy transfer and red phosphorescence in strontium aluminates co-doped with Cr3+, Eu2+ and Dy3+[J]. Journal of Luminescence, 2006,119-120:327-331.
[42]Katsumata T., Sasajima K., Nabae T., et al. Characteristics of strontium alumnate crystals used for long-duration phosphors[J]. Journal of the American Ceramic Society,1998, 81(2):413-416.
[43]Ekambaram S., Maaza M.. Combustion synthesis and luminescent properties of Eu3+-activated cheap red phosphors[J]. Journal of Alloys and Compounds,2005, 395(1-2):132-134.
[44]Diallo P. T., Boutinaud P., Mahiou R., et al. Red luminescence in Pr3+-doped calcium titanates[J]. Phys Status Solidi(a),1997,160(1):255-259.
[45]Cho S. H., Yoo J. S., Lee J. D. Synthesis and low-voltage characteristics of CaTiO3:Pr luminescent powders [J]. J.Electrochem.Soc.,1996,143(10):L231-L234.
[46]Zhang Xiyan, Cheng Guang, Mi Xiaoyun, et al. Preparation and long persistence red luminescence of Mo.2Cao.8Ti03:Pr3+(M=Mg2+,Sr2+,Ba2+,Zn2+)[J]. Journal of Rare Earths, 2004,22(1):137-139.
[47]杨志平,郭智,王文杰等.Pr3+摩尔浓度对CaTiO3:Pr3+红色长余辉材料的影响[J].功能材料与器件学报,2003,9(4)：473-476.
[48]Royce M. R., Matsuda S., Tamaki H. Red emitting long decay phosphors[P].US Patent:5650094,1997,07.22.
[49]廉世勋,林建华,苏勉曾.Ca(1-x)ZnxTiO3:Pr3+, R+(R+=Li+, Na+, K+, Rb+, Cs+, Ag+)的合成和发光 性质[J].中国稀土学报,2001，19(6)：602-605.
[50]杨志平,朱胜超,郭智等.锌对CaTiO3:Pr3+发光亮度和余辉时间的影响[J].中国稀土学报,2002,20：42-45.
[51]Jia Weiyi, Xu Wuliang, Rivera Iris, et al. Effects of compositional phase transitions on luminescenc of Sr1-xCaxTiO3:Pr3+[J]. Solid State Communication,2003,126:153-157.
[52]Weiyi Jia, Ange'lica Pe'rez-Andu'jar, Iris Rivera. Energy transfer between Bi3+ and Pr3+ in doped CaTiO3[J].Journal of the Electrochemical Society,2003,150:161-164.
[53]李秀英,廉世勋,朱爱玲等.红色长余辉发光材料Ca2Zn4Ti15O36:Pr3+的合成和发光性质[J].中国稀土学报,2005,23(1)：16-20.
[54]Pan Yuexiao, Su Qing, Xu Huifang, et al. Synthesis and red luminescence of Pr3+-doped CaTiO3 nano-phosphor from polymer precursor[J]. Journal of Solid State Chemistry, 2003,174:69-73.
[55]Dere'n P.J., Pazik R., Strek W, et al. Synthesis and spectroscopic properties of CaTiO3 nanocrystals doped with Pr3+ ions[J]. Journal of Alloys and Compounds,2008, 451:595-599.
[56]Yan Bing, Zhou Kun. In situ sol-gel composition of inorfanic/organic polymeric hybrid precursors to synthesize red-luminescence CaTiO3:Pr3+ and CaTi0.5Zr0.5O3:Pr3+ phosphors[J].Journal of Alloys and Compounds,2005,398:165-169.
[57]Yin Shengyu, Chen Donghua, Tang Wanjun. Combustion synthesis and luminescent properties of CaTiO3:Pr,Al persistent phosphors[J].Journal of Alloys and Compounds, 2007,441:327-331.
[58]尚用甲,郑峰.草酸盐共沉淀法制备CaTiO3:Pr3+长余辉发光材料的性能研究[J].功能材料,2009,40(1):17-19.
[59]Zhang Xianmin, Zhang Jiahua, Ren Xinguang, et al. The dependence of persistent phosphorescence on annealing temperatures in CaTiO3:Pr3+ nanoparticles prepared by a coprecipitation technique[J].Journal of Solid State Chemistry,2008,181:393-398.
[60]Yun Chan Kang, Jeong Su Choi, Seung Bin Park, et al. Preparation of CaTiO3:Pr phosphor by spraypyrolysis using filterexpansion aerosolgeneator[J]. Journal of Aerosol Science,1997,28:541-542.
[61]Kim K.H., Park J.K., Kim C.H., et al. Synthesis of SrTiO3:Pr,Al by ultrasonic spray pyrolysis[J]. Ceramics International,2002,28:29-36.
[62]Boutinaud P., Pinel E., Mahiou R. Luminescence and afterglow in CaTiO3:Pr3+ films deposited by spray pyrolysis[J]. Optical Materials,2008,30:1033-1038.
[63]Tan Shuyuan, Yang Piaoping,Li Chunxia, et al.Preparation, characterization and luminescent properties of spherical CaTiO3:Pr3+ phosphors by spray pyrolysis[J]. Solid State Sciences,2010,12:624-629.
[64]He Wei, Zhang Jing, Wang Lixi, et al. Preparation and properties of nanocrystal SmBO3 by nitrate-citrate sol-gel combustion method[J]. Journal of Rare Earths,2009, 27(2):231-233.
[65]Guo Kai, Chen Haohong, Guo Xiangxin, et al. Morphology investigation of yttrium aluminum garnet nano-powders prepared by a sol-gel combustion method[J]. Journal of Alloys and Compounds,2010,500:34-38.
[66]Li Yuanyuan, Xue Lihong, Fan Lingfang, et al. The effect of citric acid to metal nitrates molar ratio on sol-gel combustion synthesis of nanocrystalline LaMnO3 powders[J]. Journal of Alloys and Compounds,2009,478:493-497.
[67]Xia Guodong, Zhou Shengming, Zhang Junji, et al. Structural and optical properties of YAG:Ce3+ phosphors by sol-gel combustion method[J]. Journal of Crystal Growth,2005, 279:357-362.
[68]Azadmanjiri J. Structural and electromagnetic properties of Ni-Zn ferrites prepared by sol-gel combustion method[J]. Materials Chemistry and Physics,2008,109:109-112.
[69]Diallo P. T., Jeanlouis K., Boutinaud P., et al. Improvement of the optical performances of Pr3+ in CaTiO3[J]. Journal of Alloys and Compounds,2001,323-324:218-222.
[70]Yamamoto H., Matsuzawa T. Mechanism of Long Phosphorescence of SrAl2O4:Eu2+,Dy3+ and CaAl2O4:Eu2+,Nd3+[J]. Journal of Luminescence,1997,72-74:287-289.
[71]Aitasalo T., Deren P., Holsa J., et al. Persistent Luminescence Phenomena in Materials Doped with Rare Earth Ions [J]. Journal of Solid State Chemistry,2003,171:114-122.
[72]Chen R. Glow curves with general order kinetics[J]. Electrochem. Soc. Solid State.,1969, 116:1254-1257.
[73]McKeever S. W. S. Thermoluminescence of Solids[M]. One Edition, Published by the Press Syndicate of the University of Cambridge,1985:87-90.
[74]Manam J., Das S. Preparation, characterization and thermally stimulated luminescence studies of undoped, Cu and Mn doped SrSO4 compounds[J]. Optical Materials,2009, 31:1231-1241.
[75]Manam J., Sharma S. K. Evaluation of trapping parameters of thermally stimulated luminescence glow curves in Cu-coped Li2B4O7 phosphor[J]. Radiation Physics and Chemistry,2005,72:423-427.
[76]Haranath D., Virendra Shanker, Harish Chander etal.Studies on the decay characteristics of strontium aluminate phosphor on thermal treatment [J]. Materials Chemistry and Physics,2003,78(1):6-10.
[77]李建宇.稀土发光材料及其应用[M].北京：化学工业出版社,2003：124-125.
[78]沈雷军,赵增祺,韩莉等.Zn, Cd对CaTiO3:Pr3+的发光性质的影响[J].发光学报,2007,28(1)：74-78.
[79]Chander H., Shanker V., Ghosh P.K.. In:Proceedings of the International Symposium on Lumin. and its Appl., February 2000, p.134.
[80]Shanker V., Chander H., Ghosh P.K.. In:Proceedings of the International Symposium on Lumin. and its Appl., February 2000, p.96.
[2]Qiu J., Miura K., Inouye H., et al. Femtosecond laser induced three dimensional bright and long lasting phosphorescence inside calcium aluminosilicate glasses doped with rare earth ions[J]. Applied Physics Letters,1998,73:1763-1765.
[3]Kowatari M., Koyama D., Satoh Y., et al. The temperature dependence of luminescence from a long lasting phosphors exposed to ionizing radiation [J]. Nuclear Instruments and Methods in Physics Research A,2002,480:431-439.
[4]Sung Mook Chung, Sang hyuk Han, Kuk Hyun Song, et al. Luminescent properties of CaTiO3:Pr3+ thin-film phosphor deposited on ZnO/ITO/glass substrate[J]. Journal of Luminescence,2005,114:227-233.
[5]Sato K., Komuro S.,Morikawa T.,et al. Long afterglow characteristics of thin film phosphor fabricated by laser ablation[J].Journal of Crystal Growth,2005,275:137-141.
[6]Pinel Eric, Boutinaud Philippe, Bertrand Genevieve, et al. Preparation and characterization of luminescent films of Pr3+-doped CaTiO3 processed by sol-gel technique[J]. Journal of Alloys and Compounds,2004,374:202-206.
[7]杨志平,刘冲,郭智等.CaTiO3:Pr3+长余辉玻璃的制备与发光性能[J].发光学报,2005,26(4)：493-496.
[8]朱爱玲,廉世勋,李承志等.绿色长余辉发光玻璃的合成和性质[J].光谱实验室,2003,20(1)：23-27.
[9]Lin Yuanhua, Tang Zilong, Zhang Zhongtai, et al. Preparation and properties of photoluminescent rare earth doped SrO-MgO-B2O3-SiO2 glass[J]. Materials Science and Engineering:B,2001,86:79-82.
[10]Chang Chengkang, Mao Dali, Shen Jianfeng, et al. Preparation of long persistent SrO·2Al2O3 ceramics and their luminescent properties [J]. Journal of Alloys and Compounds,2003,348:224-230.
[11]Chang C.K., Jiang L., Mao D.L., et al. Photoluminescence of 4Sr0.7Al2O3 ceramics sintered with the aid of B2O3[J]. Ceramics International,2004,30:285-290.
[12]Jia Yi, Ye Ming, Jia Weiyi. Stress-induced mechanoluminescence in SrAl2O4:Eu2+,Dy3+[J]. Optical Materials,2006,28(9):974-979.
[13]Zhao Changliang, Chen Donghua, Yuan Yuhong, et al. Synthesis of Sr4Al14O25:Eu2+, Dy3+ phosphor nanometer powders by combustion processes and its optical properties[J]. Materials Science and Engineering:B,2006,133(3):200-204.
[14]薛红伟,崔彩娥,黄平等.烧结温度对蓝色长余辉材料Sr2Al6O11:Eu2+,Dy3+发光性能的影响[J].人工晶体学报,2009,38(6)：1384-1387.
[15]Jia Weiyi, Yuan Huabiao, Lu Lizhu, et al. Phosphorescent dynamics in SrAl2O4:Eu2+,Dy3+ single crystal fibers[J]. Journal of Luminescence,1998,76-77:424-428.
[16]Tang Jinfeng, Yu Xibin, Yang Liangzhun, et al. Preparation and Al3+ enhanced photoluminescence properties of CaTiO3:Pr3+[J].Materials Letters,2006,60:326-329.
[17]Zhang Juncheng, Wang Xusheng, Yao Xi. Enhancement of luminescence and afterglow in CaTiO3:Pr3+ by Zr substitution for Ti[J]. Journal of Alloys and Compounds,2010, 498:152-156.
[18]Wang Rong, Meng Jianxin. Hydrothermal preparation and characterization of long-afterglow phosphors CaTiO:Pr,Al [J]. Journal of the Chinese Rare Earth Society, 2009,27(3):349.
[19]Wang Xusheng, Xu Chaonan, Yamada Hiroshi. Enhancement of photoluminescence in CaTiO3:Pr3+ by Ba and Sr substitution for Ca [J].Jpn. J. Appl. Phys.2005,44:L912.
[20]张英兰,赵绪义,葛中久.Dy3+在Ca1-xSrxS:Eu2+,Er3+中的光致发光特性[J].吉林大学自然科学学报,1997,4：52-54.
[21]贾冬冬,姜联合,刘玉龙等.CaxSr1-xS:Bi,Tm,Cu和 CaS:Eu荧光材料的研究[J].发光学报,1998,19(4)：312-316.
[22]戴国瑞,郑燕,张英兰.非放射性红色发光材料的合成与发光[J].吉林大学学报(理学版),1993,1：97-100.
[23]袁曦明,许永胜,于江波等.红色长余辉发光材料CaS:Eu2+,Tm3+的制备研究[J].材料开发与应用,2002,17(3)：21-24.
[24]肖志国.硫化物长余辉发光材料及制造方法[P].中国专利：CN97111381,1997.
[25]Murazaki Y, Arak K, Ichinomiya K. A new long persistence red phosphor [J]. Japanese Rare Earth (in Japan),1999,35:41-45.
[26]李灿涛,袁剑辉,张万锴等.掺杂Gd3+对Y2O2S:Eu3+发光特性的影响[J].发光学报,1999,20(4)：316-319.
[27]宋春燕,雷炳富,刘应亮等.Eu3+在La2O2S中的长余辉发光[J].无机化学学报,2004,20(1)：89-93.
[28]宋春燕,王晓华,刘应亮等.新型橙红色长余辉发光材料Gd2O2S:Sm3+的合成[J].化学通报,2004,5：373-376.
[29]宋春燕,刘应亮,张静娴等.微波法合成橙红色长余辉磷光粉Gd2O2S:Sm3+[J].暨南大学学报(自然科学版),2003,24(5)：93-96.
[30]Wang Xiaoxin, Zhang Zhongtai, Tang Zilong, et al. Characterization and properties of a red and orange Y2O2S-based long afterglow phosphor [J]. Materials chemistry and physics,2003,80(1):1-5.
[31]Lei Bingfu, Liu Yingliang, Tang Gongben, et al. Spectra and long lasting properties of Sm3+ doped yttrium oxysulfide phosphor [J]. Materials chemistry and physics,2004, 87(1):227-232.
[32]杨志平,郭智,王文杰等.Y2O2S:Eu3+,Mg2+,Ti4+红色材料的制备和长余辉性能[J].发光学报,2004,25(2)：183-187.
[33]Wang Xiaojun, Jia Dongdong, Yen W.M. Mn2+activated green, yellow, and red long persistent phosphors [J]. Journal of Luminescence,2003, (102-103):34-37.
[34]Lei Bingfu, Liu Yingliang, Liu Jie, et al. Pink light emitting long lasting phosphorescence in Sm3+ doped CdSiO3 [J], Journal of Solid State Chemistry.2004,177(4-5):1333-1337.
[35]Lei Bingfu, Liu Yingliang, Ye Zeren, et al.Luminescence properties of CdSiO3：Mn2+ phosphor [J]. Journal of Luminescence,2004,109(3-4):215-219.
[36]Froelich H.C. Strontium Aluminate Phosphor [P], US Patent:2392814,1946.
[37]Palilla F.C., Luvine A.K., Tonikus M.R.. Fluoerscent Properties of alkaline earth aluminates of the type MAl2O4 activated by divalent europium [J]. Journal of The Electrochemical Society,1968,115(6):642-648.
[38]Pallavi Page, Rahul Ghildiyal, Murthy K.V.R.. Synthesis, characterization and luminescence of Sr2Al2O6 phosphor with trivalent rare earth dopant [J],Materials Research Bulletin,2006,41(10):1854-1860.
[39]Zhang Ping, Xu Mingxia. Zheng Zhentai, et al. Microwave synthesis and characterization of new red long afterglow phosphor Sr3Al2O6:Eu [J]. Transactions of Nonferrous Metals Society of China,2006,16:423-425.
[40]Pan Yuexiao, Herman H.-Y.Sung, Wu Hao, et al, Hydrothermally-mediated preparation and photoluminescent properties of Sr3Al2O6:Eu3+ phosphor [J]. Materials Research Bulletin,2006,41(2):225-231.
[41]Zhong Ruixia, Zhang Jiahua, Zhang Xia,et al. Energy transfer and red phosphorescence in strontium aluminates co-doped with Cr3+, Eu2+ and Dy3+[J]. Journal of Luminescence, 2006,119-120:327-331.
[42]Katsumata T., Sasajima K., Nabae T., et al. Characteristics of strontium alumnate crystals used for long-duration phosphors[J]. Journal of the American Ceramic Society,1998, 81(2):413-416.
[43]Ekambaram S., Maaza M.. Combustion synthesis and luminescent properties of Eu3+-activated cheap red phosphors[J]. Journal of Alloys and Compounds,2005, 395(1-2):132-134.
[44]Diallo P. T., Boutinaud P., Mahiou R., et al. Red luminescence in Pr3+-doped calcium titanates[J]. Phys Status Solidi(a),1997,160(1):255-259.
[45]Cho S. H., Yoo J. S., Lee J. D. Synthesis and low-voltage characteristics of CaTiO3:Pr luminescent powders [J]. J.Electrochem.Soc.,1996,143(10):L231-L234.
[46]Zhang Xiyan, Cheng Guang, Mi Xiaoyun, et al. Preparation and long persistence red luminescence of Mo.2Cao.8Ti03:Pr3+(M=Mg2+,Sr2+,Ba2+,Zn2+)[J]. Journal of Rare Earths, 2004,22(1):137-139.
[47]杨志平,郭智,王文杰等.Pr3+摩尔浓度对CaTiO3:Pr3+红色长余辉材料的影响[J].功能材料与器件学报,2003,9(4)：473-476.
[48]Royce M. R., Matsuda S., Tamaki H. Red emitting long decay phosphors[P].US Patent:5650094,1997,07.22.
[49]廉世勋,林建华,苏勉曾.Ca(1-x)ZnxTiO3:Pr3+, R+(R+=Li+, Na+, K+, Rb+, Cs+, Ag+)的合成和发光 性质[J].中国稀土学报,2001，19(6)：602-605.
[50]杨志平,朱胜超,郭智等.锌对CaTiO3:Pr3+发光亮度和余辉时间的影响[J].中国稀土学报,2002,20：42-45.
[51]Jia Weiyi, Xu Wuliang, Rivera Iris, et al. Effects of compositional phase transitions on luminescenc of Sr1-xCaxTiO3:Pr3+[J]. Solid State Communication,2003,126:153-157.
[52]Weiyi Jia, Ange'lica Pe'rez-Andu'jar, Iris Rivera. Energy transfer between Bi3+ and Pr3+ in doped CaTiO3[J].Journal of the Electrochemical Society,2003,150:161-164.
[53]李秀英,廉世勋,朱爱玲等.红色长余辉发光材料Ca2Zn4Ti15O36:Pr3+的合成和发光性质[J].中国稀土学报,2005,23(1)：16-20.
[54]Pan Yuexiao, Su Qing, Xu Huifang, et al. Synthesis and red luminescence of Pr3+-doped CaTiO3 nano-phosphor from polymer precursor[J]. Journal of Solid State Chemistry, 2003,174:69-73.
[55]Dere'n P.J., Pazik R., Strek W, et al. Synthesis and spectroscopic properties of CaTiO3 nanocrystals doped with Pr3+ ions[J]. Journal of Alloys and Compounds,2008, 451:595-599.
[56]Yan Bing, Zhou Kun. In situ sol-gel composition of inorfanic/organic polymeric hybrid precursors to synthesize red-luminescence CaTiO3:Pr3+ and CaTi0.5Zr0.5O3:Pr3+ phosphors[J].Journal of Alloys and Compounds,2005,398:165-169.
[57]Yin Shengyu, Chen Donghua, Tang Wanjun. Combustion synthesis and luminescent properties of CaTiO3:Pr,Al persistent phosphors[J].Journal of Alloys and Compounds, 2007,441:327-331.
[58]尚用甲,郑峰.草酸盐共沉淀法制备CaTiO3:Pr3+长余辉发光材料的性能研究[J].功能材料,2009,40(1):17-19.
[59]Zhang Xianmin, Zhang Jiahua, Ren Xinguang, et al. The dependence of persistent phosphorescence on annealing temperatures in CaTiO3:Pr3+ nanoparticles prepared by a coprecipitation technique[J].Journal of Solid State Chemistry,2008,181:393-398.
[60]Yun Chan Kang, Jeong Su Choi, Seung Bin Park, et al. Preparation of CaTiO3:Pr phosphor by spraypyrolysis using filterexpansion aerosolgeneator[J]. Journal of Aerosol Science,1997,28:541-542.
[61]Kim K.H., Park J.K., Kim C.H., et al. Synthesis of SrTiO3:Pr,Al by ultrasonic spray pyrolysis[J]. Ceramics International,2002,28:29-36.
[62]Boutinaud P., Pinel E., Mahiou R. Luminescence and afterglow in CaTiO3:Pr3+ films deposited by spray pyrolysis[J]. Optical Materials,2008,30:1033-1038.
[63]Tan Shuyuan, Yang Piaoping,Li Chunxia, et al.Preparation, characterization and luminescent properties of spherical CaTiO3:Pr3+ phosphors by spray pyrolysis[J]. Solid State Sciences,2010,12:624-629.
[64]He Wei, Zhang Jing, Wang Lixi, et al. Preparation and properties of nanocrystal SmBO3 by nitrate-citrate sol-gel combustion method[J]. Journal of Rare Earths,2009, 27(2):231-233.
[65]Guo Kai, Chen Haohong, Guo Xiangxin, et al. Morphology investigation of yttrium aluminum garnet nano-powders prepared by a sol-gel combustion method[J]. Journal of Alloys and Compounds,2010,500:34-38.
[66]Li Yuanyuan, Xue Lihong, Fan Lingfang, et al. The effect of citric acid to metal nitrates molar ratio on sol-gel combustion synthesis of nanocrystalline LaMnO3 powders[J]. Journal of Alloys and Compounds,2009,478:493-497.
[67]Xia Guodong, Zhou Shengming, Zhang Junji, et al. Structural and optical properties of YAG:Ce3+ phosphors by sol-gel combustion method[J]. Journal of Crystal Growth,2005, 279:357-362.
[68]Azadmanjiri J. Structural and electromagnetic properties of Ni-Zn ferrites prepared by sol-gel combustion method[J]. Materials Chemistry and Physics,2008,109:109-112.
[69]Diallo P. T., Jeanlouis K., Boutinaud P., et al. Improvement of the optical performances of Pr3+ in CaTiO3[J]. Journal of Alloys and Compounds,2001,323-324:218-222.
[70]Yamamoto H., Matsuzawa T. Mechanism of Long Phosphorescence of SrAl2O4:Eu2+,Dy3+ and CaAl2O4:Eu2+,Nd3+[J]. Journal of Luminescence,1997,72-74:287-289.
[71]Aitasalo T., Deren P., Holsa J., et al. Persistent Luminescence Phenomena in Materials Doped with Rare Earth Ions [J]. Journal of Solid State Chemistry,2003,171:114-122.
[72]Chen R. Glow curves with general order kinetics[J]. Electrochem. Soc. Solid State.,1969, 116:1254-1257.
[73]McKeever S. W. S. Thermoluminescence of Solids[M]. One Edition, Published by the Press Syndicate of the University of Cambridge,1985:87-90.
[74]Manam J., Das S. Preparation, characterization and thermally stimulated luminescence studies of undoped, Cu and Mn doped SrSO4 compounds[J]. Optical Materials,2009, 31:1231-1241.
[75]Manam J., Sharma S. K. Evaluation of trapping parameters of thermally stimulated luminescence glow curves in Cu-coped Li2B4O7 phosphor[J]. Radiation Physics and Chemistry,2005,72:423-427.
[76]Haranath D., Virendra Shanker, Harish Chander etal.Studies on the decay characteristics of strontium aluminate phosphor on thermal treatment [J]. Materials Chemistry and Physics,2003,78(1):6-10.
[77]李建宇.稀土发光材料及其应用[M].北京：化学工业出版社,2003：124-125.
[78]沈雷军,赵增祺,韩莉等.Zn, Cd对CaTiO3:Pr3+的发光性质的影响[J].发光学报,2007,28(1)：74-78.
[79]Chander H., Shanker V., Ghosh P.K.. In:Proceedings of the International Symposium on Lumin. and its Appl., February 2000, p.134.
[80]Shanker V., Chander H., Ghosh P.K.. In:Proceedings of the International Symposium on Lumin. and its Appl., February 2000, p.96.