摘要
本论文采用不同的化学方法分别合成了三种基于钼酸盐的发光材料:可紫外和可见蓝光区域激发的AgLaMo2O8:Pr3+荧光粉、BaLa2(MoO4)4:Pr3+荧光材料和纳米组装的CaMoO4:Eu3+/Na+荧光粉。应用X‐射线粉末衍射(XRD)、荧光光谱(PL)、场发射扫描电子显微镜(FESEM)、扫描电子显微镜(SEM)、透射电子扫描显微镜(TEM)等测试手段分别对材料的结构、形貌和性能进行表征,研究了不同反应条件对所得材料的晶型结构、形貌以及光学性能的影响,得到了最佳制备工艺条件,并对相关合成机理和发光机理进行了解释和讨论。主要研究内容叙述如下:
1.通过一种简便的高温固相法成功合成了AgLaMo2O8:Pr3+红色荧光粉,讨论了合成荧光粉的最佳工艺条件,并研究了不同反应条件对物质结晶性能和发光性能的影响。通过各项表征结果可知:该发光材料粒径在1µm以下,在430～500nm的光谱区间有很好的吸收,与商业蓝光LED的发射波长相一致,并在以649 nm为中心的红光区有很强的发射,其发光强度约是商业红粉Y2O2S:Eu3+发光强度的3.2倍。此外,发光性能受到反应温度和激活剂掺杂浓度的影响,镨离子最佳摩尔浓度是3%,最优化的温度是1100℃。在649 nm处的半峰宽仅有3 nm,红色纯度很高,其色坐标指数是(0.685,0.315),表明钼酸银镧掺镨红色荧光体能有效地改善白光LED的显色性。
2.同样利用简单的固相反应法制备BaLa2(MoO4)4:Pr3+红色荧光材料,研究了其在各制备条件下的影响,其物理化学性能与之前制备的AgLaMo2O8:Pr3+相似。但在制备过程中加入碱金属卤化物,从而在材料中引入了碱金属离子,成功地制备了碱金属掺杂的BaLa2(MoO4)4:Pr3+荧光材料。其中,碱金属的引入加大了钼酸盐离子晶体结构的非对称性。引入碱金属后,荧光材料的发光性能得到了大幅度地改善,是掺杂前BaLa2(MoO4)4:Pr3+荧光材料发光强度的1.35倍。
3.利用一种方便,环保,无任何有机添加剂的低成本的水热方法制备了自组装多级结构CaMoO4:Eu3+,Na+荧光体。由SEM,FE‐SEM和TEM表征照片知:在150°C‐ 6 h‐ pH1.5的反应条件下合成的钼酸盐样品颗粒平均直径为5µm,其结构是纳米片一层一层叠加而成的三维圆球和圆盘状。我们通过温度实验探讨了多级结构的形成机制,利用Ostwald熟化和自组装聚集机制对晶体生长进行了解释。此外,本章中还研究了pH值和钙源等反应条件对产物形貌和分散性的影响,得出了pH值在1.5和CaNO3做钙源时为这些材料的最佳条件。在激发光谱图中,激发波长范围从350到530nm的紫外和可见光区,显著的扩展了发光材料的应用区域。同时,该钼酸钙荧光材料中存在的少量Na+离子能够起到电荷补偿的作用,提高了材料的发光性能。发射光谱表明,样品发出了明亮的红色荧光,且具有较高的色纯度.
In this study, the AgLaMo2O8:Pr3+ and BaLa2(MoO4)4:Pr3+ andCaMoO4:Eu3+/Na+phosphorswitharatherstrongf‐ftransitionexcitationintheUVandvisibleregionwerefabricatedbydifferentsynthesismethods.Inaddition,thestructures, morphologies and optical properties of as‐prepared products werethoroughlycharacterizedbyusingX‐raypowderdiffraction(XRD),Scanningelectronmicroscopy(SEM),Fieldmissionscanningelectronmicroscopy(FESEM),Transmissionelectron scanning microscopy (TEM), and Fluorescence spectroscopy (PL),respectively.Here,theeffectsofthesynthesismethodsandreactionconditionsonthestructure,morphologyandopticalpropertiesofas‐preparedsampleshavebeenstudied. Finally, the optimal preparation conditions, the related mechanisms ofsynthesis and luminescence mechanism were explained and discussed. The mainresultsaresummarizedasfollowing:
1) The red phosphors AgLaMo2O8:Pr3+ were prepared by conventionalsolid‐statereactiontechnique.TheeffectsofsynthesistemperatureandPr3+dopedconcentrationontheluminescentpropertiesandcrystalstructuresofredphosphorshave been investigated. The detailed results indicate: The diameter of phosphorparticlesislessof1µm.InthePLspectraofas‐preparedsamples,theoptimalvalueofPr3+concentrationis3%andtheoptimizedtemperatureis1100Cforthestrongestemission.Theexcitationwavelengthranging430nm–500nminthevisibleregioncoverstheavailablerangeofcommercialblueLED.Moreover,thePLspectrashowsasatisfactoryredperformanceat649nmwiththeFWHMof3nmandthe CIE chromaticity coordinates is (0.685, 0.315), indicating this phosphor caneffectivelyimprovecolorrenderingindexofwhiteLED.
2)The deep red phosphors BaLa2(MoO4)4:Pr3+ have been prepared by thesame solid‐state reaction technique. The effects of reaction conditions on theluminescent properties and crystal structures of compound have also beeninvestigated.Itsphysicalandchemicalpropertiesandphotoluminescencearesimilarwith AgLaMo2O8:Pr3+. But the alkali metal were introduced into the phosphor system BaLa2(MoO4)4:Pr3+ by adding appropriate amounts of alkali halide in thepreparing.Thedopingalkalimetalionscanincreasethenoncentrosymmetryofthecrystalstructureofmolybdate.TheredemissionintensitywasenhancedsignificantlybydopingalkalimetalintheBaLa2(MoO4)4:Pr3+phosphorsystemandtheemissionintensityis1.35timescomparedwiththatofundopedalkalimetal.
3)The Eu3+/Na+‐codoped CaMoO4 microphosphors were successfullysynthesizedatlowtemperatureviaafacilehydrothermalmethodinsurfactant‐freeenvironment.SEM,FE‐SEMandTEMimagesoftheCaMoO4productspreparedatpH1.5,150°Cfor6hrevealed3Dflake‐ballandflake‐disksuperstructures,composedofdenselypackednanoflakes.TheformationmechanismofCaMoO4microstructureswas discussed in detail based on the hydrothermal temperature. Meanwhile, theaffect of pH value and Ca source on the morphology and photoluminescencepropertieswerealsoinvestigated.Room‐temperaturephotoluminescencepropertiesofmicrosizedCaMoO4:Eu3+/Na+phosphorswerestudied.Itsexcitationwavelengthsrangingfrom350to530nmintheUVandvisibleregionssignificantlyextendtheexcitation region of phosphor materials. Comparison with Eu3+‐doped sample,Eu3+,Na+‐codoped CaMoO4 samples play more stronger photoluminescenceintensity,whereNa+actsasachargecompensator.ThiscanbeexplainedbychargecompensationinthephosphorsystemCaMoO4:Eu3+/Na+.ThePLspectraindicatetheproductsemitbrightredfluorescenceandhavehighcolorpurity.
引文
[1]许洁瑜.,中国有色金属报, 2006, 003.
[2]张文钲.,钼业经济技术, 1991, 4, 50.
[3]王永刚., [硕士学位论文].山东:中国海洋大学, 2006.
[4] Wang Z L, Liang H B, Zhou L Y, et al., Journal of luminescence, 2008, 128, 147.
[5] Liya Zhou, Jianshe Wei, Fuzhong Gong, Junli Huang, Linghong Yi, Journal of Solid State Chemistry, 2008, 181, 1337.
[6] Wang Z L, Wang J, Liang H B, et al, Materials Research Bulletin, 2008, 43, 907.
[7] Wang Z L, Liang H B, Gong M L, et al., Journal of Alloys and Compounds, 2007, 432, 308.
[8]张国有,赵晓霞,孟庆裕等,发光学报, 2006, 26, 724.
[9]张国有,赵晓霞,孟庆裕等,发光学报, 2007, 28, 57.
[10] Wang X X, Xian Y L, Wang G, et al., Optical Materials, 2007, 30, 521.
[11] Zhai X X, Wang X J, Chen B J, et al., Journal of Alloys and Com- pounds, 2007, 433, 352.
[12]吴洪鹏,颜鲁婷,王鹏,司文捷,稀有金属材料与工程, 2009, 38, 2065.
[13] Toki H,Sato Y, Tamura K, et al., Proceedings of the Third International Display Workshop.2, 1996, 919.
[14]李涛,苏州大学硕士论文, 2008.
[15]孙彦彬,邱关明,陈永杰等,稀土, 2003, 24, 43k.
[16]陈磊,陈建敏,周惠娣.,材料科学与工程学报, 2004, 22, 138.
[17]连洪洲,石春山,化学通报2004, 5, 333.
[18]阎建辉,黄可龙,戴潇燕,精细化工中间体2003, 33, 4.
[19]孙进高,王广凤,尉艳,方宾,稀有金属快报, 2005, 24, l.
[20]杨定明,朱达川,戴亚堂等,稀有金属材料与工程, 2005, 34, 436.
[21] Xun W,Sun X,Zou B,Li Y, Adv. Mater., 2003,15, 1442.
[22] Fang Y P,Xu A W,You L P,Song R Q,Yu J C,Zhang H X,Li Q,Liu H Q., Adv. Funct. Mater., 2003, 13, 955.
[23]施尔畏,夏长泰,王步国等,无机材料学报, 1996, 2, 67.
[24] Thomas Baby, V. P. N. Nampoori , Solid State Communications, 1992, 81, 367.
[25] Jie Liu, Hongzhou Lian, Jiayue Sun, Chunshan Shi, Chemistry Letters, 2005, 34, 1340.
[26] C. Chartier, C. Barthou, P. Benalloul, J.M. Frigerio, 2005, 111, 147.
[27] Yunsheng Hu, Weidong Zhuang, Hongqi Ye, Donghui Wang, Journal of Alloys and Compounds, 2005, 390, 226.
[28] Hong He, Renli Fu, Xiufeng Song, Deliu Wang, Jiankang Chen, Journal of Luminescence, 2008, 128, 489.
[29] H. Masui, S. Nakamura, Encyclopedia of Materials: Science and Technology, 2008, 1.
[30] H. S. Jang, W. B. Im, D. C. Lee, D. Y. Jeon, S. S. Kim, Journal of Luminescence, 2007, 126, 371.
[31] Ho Seong Jang, Heesun Yang, Sung Wook Kim, Ji Yeon Han, Sang-Geun Lee, and Duk Young Jeon, Adv. Mater., 2008, 9999, 1.
[32] Gao P, Xie Y, Xie L, et al., Chem. Lett., 2006, 35, 162.
[33] Chen Y, Wang Y S, Chen D Q et al., Phys. Chem. B, 2005, 109, 794.
[34] Xu Y P, Jiang D Y, Shi J L. et al., Chem. Lett., 2005, 34, 978.
[35] Yu J Q, Kudo A, Chem. Lett., 2005, 34, 1528.
[36] Kwan S, Kim F, Akana J, et al., Chem.Commun., 2001, 5, 447.
[37] Shi H T, Qi L M, Ma J M, et al., Adv. Funct. Mater., 2005, 15, 442.
[38] Gong Q, Qian X F, Cao H L, et al., 19295.
[39] Huang J H, Gao L, Journal of the American Ceramic Society, 2006, 89, 3877.
[40] Afanasiev P, Mater. Lett., (2007), doi:10.1016/j.matlet.2007.02.061.
[41] Narukawa Y, Narita J, Sakamoto T, et al., Phys. Stat., 2007, 204, 2087.
[42] Yuji U, Optical Engineering, 2005, 44, 124003.
[43] Jia D, Hunter D. N., Journal of applied physics, 2006, 100, 113125.
[44] Xiao-Mei Zhang, Ming-Yen Lu, Yue Zhang, Lih-J. Chen, Zhong Lin Wang, Adv. Mater., 2009, 21, 1.
[45]徐时清,金尚忠,王宝玲等,中国计量学院学报, 2006, 17, 188.
[46]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, 477.
[47]张凯,刘河洲,胡文彬,材料导报, 2005, 19, 50.
[48]刘行仁.白光LED固态照明光转换荧光体[J],发光学报, 2007, 28(3), 291.
[49]王涛,井艳军,朱月华等,中国照明电器, 2008, 2, 16.
[50]杨水金,孙聚堂,秦子斌,稀土, 1999, 20, 62.
[51] Wang Z L, Liang H B, Gong M L, et al., Materials Letters, 2008, 62, 619.
[52]张国有,赵晓霞,孟庆裕等,发光学报, 2006, 26, 724.
[53]张国有,赵晓霞,孟庆裕等,发光学报, 2007, 28, 57.
[54] Wang Z L, Liang H B, Wang J, et al., Appl. Phys. Lett., 2006, 89, 071921.
[55] Wang Z L, Liang H B, Gong M L, et al. , Electrochem. Solid State Lett., 2005, 8, H33.
[56] Xuyong Yang, Jie Liu, Hong Yang, XiBin Yu, Yuzhu Guo, Yongqin Zhou, Jieyu Liu, J. Mater. Chem., 2009, 19, 3771.
[57] Chongfeng Guo, Dexiu Huang, Qiang Su, Materials Science and Engineering B, 2006, 130, 189.
[58] I. W. Park,J. H. Kim, J. S. Yoo, H. H. Shin,C. K. Kim, and C. K. Choi, J. Elechem. Soc., 2008, 155, G132.
[59] Yunsheng Hu, Weidong Zhuang, Hongqi Ye, Shusheng Zhang et al. J. Lumin., 2005, 111, 139.
[60] Thomas Baby, V. P. N. Nampoori, Solid State Communications, 1992, 81, 367.
[61] J. Thirumalai, R. Jagannathan, D.C. Trivedi, J. Lumin., 2007, 126, 353.
[62] Mariyam Thomas, P. Prabhakar Rao, M.Deepa, M.R.Chandran, Peter Koshy, J. Solid State Chem., 2009, 182, 203.
[63] Md. Masuqul Haque, Dong-Kuk Kim, Materials Letters, 2009, 63, 793.
[64] Li-Ya Zhou, Jian-She Wei, Ling-Hong Yi, Fu-Zhong Gong, Jun-Li Huang, Wei Wang, Materials Research Bulletin, 2009, 44, 1411.
[65] Jie Liu, Hongzhou Lian, Chunshan Shi, Optical Materials, 2007, 29, 1591.
[66] Xuyong Yang, XiBin Yu, Hong Yang, Yuzhu Guo, Yongqin Zhou, J. Alloys Compd., 2009, 479, 307.
[67] Enrico Cavalli, Philippe Boutinaud, Marco Bettinelli, Pieter Dorenbos, J. Solid State Chem., 2008, 181, 1025.
[68] Xiao-xiao Wang, Yu-lun Xian, Gang Wang, Jian-xin Shi, Qiang Su, Meng-lian Gong, Optical Materials, 2007, 30, 521.
[69] Santa Chawla, Nitin Kumar, Harish Chander, J. Lumin., 2009, 129, 114.
[70] V. Sivakumar and U. V. Varadaraju, J. Electrochem. Soc., 2006, 153, H54.
[71] Chongfeng Guo, Fei Gao, Lifang Liang, Byung Chun Choi, Jung-Hyun Jeong, J. Alloys Compd., 2009, 479, 607.
[72] Hiroshi Takashima, Kohei Shimada, Noboru Miura, Tetsuhiro Katsumata, Yoshiyuki Inaguma, Kazushige Ueda, Mitsuru Itoh, Adv. Mater., 2009, 21, 1.
[73] Wei Li, Joonho Lee, J. Phys. Chem.C, 2008, 112, 11679.
[74] Wang Z L, Wang J, Liang H B, et al., Materials Research Bulletin, 2008, 43, 907.
[75] Wang X X, Xian Y L, Wang G, et al., Optical Materials, 2007, 30, 521.
[76] Zhai X X, Wang X J, Chen B J, et al., Journal of Alloys and Com- pounds, 2007, 433, 352.
[77]Wang Z L, Liang H B, Zhou L Y, et al., Journal of luminescence, 2008, 128, 147.
[78] Liya Zhou, Jianshe Wei, Fuzhong Gong, Junli Huang, Linghong Yi, Journal of Solid State Chemistry, 2008, 181, 1337.
[79] Wang Z L, Liang H B, Gong M L, et al., Journal of Alloys and Compounds, 2007, 432, 308.
[80]王永刚, [硕士学位论文],山东:中国海洋大学,2006.
[81]张国有,赵晓霞,孟庆裕等,发光学报, 2006, 26, 724.
[82]张国有,赵晓霞,孟庆裕等,发光学报, 2007, 28, 57.
[83] Jie Liu, Hongzhou Lian, and Chunshan Shi, Optical Materials, 2007, 29, 1591.
[84] ZhanHui Zhang, Qiang Huang, Xu Zhao, and ZhiLiang Huang, Phys. Status Solidi A 2009, DOI: 10.1002.
[85] Xuyong Yang, Xibin Yu, Hong Yang, Yuzhu Guo, Yongqin Zhou, J.Alloys Compd., 2009, 479, 307.
[86] Tae Hwan Cho, Ho Jung Changb, Ceramics International, 2003, 29,611.
[87] Jie Liu, Hongzhou Lian, Chunshan Shi, Optical Materials, 2007, 29, 1591.
[88] Suxia Yan, Jiahua Zhang, Xia Zhang, Shaozhe Lu, Xinguang Ren, Zhaogang Nie, Xiaojun Wang, J. Phys. Chem. C, 2007, 111, 13256.
[89]肖林久,孙彦彬,邱关明等,稀土, 2002, 23, 46.
[90]郭立华.纳米稀土发光材料的研究[J],江西化工, 2005, 3, 16.
[91] Wei Li and Joonho Lee, J. Phys. Chem. C 2008, 112, 11679.
[92] Fang Lei and Bing Yan, J. Am. Ceram. Soc. 2009, 92, 1262.
[93] Yongqin Zhou, Jie Liu, Xuyong Yang, Xibin Yu, and Jie Zhuang, J. Electrochem. Soc. 2010, 157, 278.
[94] Mariyam Thomas, P. Prabhakar Rao , M. Deepa, M.R. Chandran, and Peter Koshy, J. Solid State Chem. 2009, 182, 203.
[95] Chao Zhang, Enhong Shen, Enbo Wang , Zhenhui Kang, Lei Gao, Changwen Hu, and Lin Xu, Mater. Chem. Phys. 2006, 96, 240.
[96] Wen-Shou Wang, Liang Zhen, Cheng-Yan Xu, and Wen-Zhu Shao, Cryst. Growth Des. 2009, 9, 1558.
[97] Ieda L. V. Rosa, Ana Paula A. Marques, Marcos T. S. Tanaka, Dulce M. A. Melo, 48Edson R. Leite, Elson Longo, JoséArana Varela, J. Fluoresc. 2008, 18, 239.
[98] Fang Lei and Bing Yan, J. Phys. Chem. C 2009, 113, 1074.
[99] Chunxia Li, Zhiyao Hou, Cuimiao Zhang, Piaoping Yang, Guogang Li, Zhenhe Xu, Yong Fan, and Jun Lin, Chem. Mater. 2009, 21, 4598.
[100] Fang Lei, Bing Yan, Hao-Hong Chen, Qiang Zhang, and Jing-Tai Zhao, Cryst. Growth Des. 2009, 9, 3730.
[101] LiXia Yang, YingJie Zhu, Liang Li, Ling Zhang, Hua Tong, WeiWei Wang, GuoFeng Cheng, and JieFang Zhu, Eur. J. Inorg. Chem. 2006, 4787.
[102] Ye Jin, Jiahua Zhang, Shaozhe Lu1, Haifeng Zhao, Xia Zhang, and Xiaojun Wang, J. Phys. Chem. C 2008, 112, 5860.
[103] Fang Lei and Bing Yan, J. Solid State Chem. 2008, 181, 855.
[104] Wenbo Bu, Yunpeng Xu, Na Zhang, Hangrong Chen, Zile Hua, and Jianlin Shi, Langmuir 2007, 23, 9002.
[105] Xuyong Yang, Jie Liu, Hong Yang, Xibin Yu, Yongqin Zhou, Jieyu Liu, J. Mater. Chem. 2009, 19, 3771.
[106] Jie Liu, Hongzhou Lian, and Chunshan Shi, Optical Materials 2007, 29, 1591.
[107] ZhanHui Zhang, Qiang Huang, Xu Zhao, and ZhiLiang Huang, Phys. Status Solidi A 2009, DOI: 10.1002.
[108] Meng Shang , Wenzhong Wang, Jia Ren , Songmei Sun , Lu Wang and Ling Zhang, J. Mater. Chem. 2009, 19, 6213.
[109] Xian-Luo Hu and Ying-Jie Zhu, Langmuir 2004, 20, 1521.
[110] Jeong Ho Ryu, Jong-Won Yoon, Kwang Bo Shim, J. Alloy. Comp. 2006, 413, 144.
[111] Jingyi Chen, Benjamin J. Wiley, and Younan Xia, Langmuir 2007, 23, 4120.
[112] Wenshou Wang, Yongxing Hu, James Goebl, Zhenda Lu, Liang Zhen, and Yadong Yin, J. Phys. Chem. C 2009, 113, 16414.
[113] Lisha Zhang, Wenzhong Wang, Lin Zhou, and Haolan Xu, small 2007, 3, 1618.
[114] Xiaoxiao Wang, Yulun Xian, Gang Wang, Jianxin Shi, Qiang Su, and Menglian Gong, Optical Materials 2007, 30, 521.
[115] L.S. Cavalcante, J.C.Sczancoski, R.L.Tranquilin, M.R.Joya, P.S.Pizani, J.A.Varela, E.Longo, J. Phys. Chem. Solid 2008, 69, 2674.
[116] Vale′ria M. Longo, Alberthmeiry T. de Figueiredo, Adaci B. Campos, Jose W. M. Espinosa, Anto?nio C. Hernandes, C. A. Taft, Julio R. Sambrano, Jose′A. Varela, and Elson Longo, J. Phys. Chem. A. 2008, 112, 8920.
