稀土纳米结构SiO_2发光材料的制备及性能研究
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摘要
本文采用溶胶-凝胶法和水热法制备了不同掺杂类型和不同结构的纳米Si02发光材料,通过荧光(PL)光谱、红外吸收谱(IR)、原子力显微镜(AFM)、透射电镜(TEM)等现代分析手段对样品进行了表征,并对其发光机理进行了分析。
通过研究不同含水量、退火温度等因素对样品的荧光强度,磷光强度和发光寿命等性能的影响,得知无论对于粉末还是薄膜形态的Tb3+掺杂SiO2发光材料,这些因素同时影响着Tb3+的发光性能,且对发光强度的影响形成了一个竞争机制。经750℃退火处理样品的发光强度,随含水量的增加,先减弱后增强之后又减弱。通过分析样品的磷光特性,得知含水量对磷光与荧光强度的变化趋势一致,且对发光衰减时间也有明显的影响。最终,确定正硅酸乙酯,无水乙醇和蒸馏水的最优摩尔比为1：4：4,陈化时间为一天,在650-800℃存在最佳退火温度使得样品SiO2：Re3+发光最强。
采用sol-gel法分别制备了Zn2+、Sn2+和Al3+等金属离子掺杂的SiO2：Re3+发光干凝胶和薄膜,薄膜分别镀在玻璃片和硅片上。充分利用F-7000荧光光谱仪分析了不同金属离子掺杂SiO2：Re3+样品的发光性能。通过掺杂金属离子改变稀土离子的微观环境使得样品SiO2：Re3+,Mn+发光效率增大。同等条件下,粉末发光最强,玻璃上镀的薄膜发光强度次之,硅片上镀的薄膜发光最弱。由于局域场增强或能量转移效应,金属离子掺杂SiO2：Re3+样品发光较不掺杂的强；金属离子掺杂样品所需的最佳退火温度比无掺杂样品的有所降低；不同类型金属离子掺杂SiO2：Re3+样品发光最强时对应的最佳浓度不同,如当Re是Tb时,Zn2+掺杂的最佳浓度为0.4%,而Sn2+为0.2%。此外,比较了利用水热法和溶胶凝胶法制备得到SiO2：Tb3+,Zn2+样品的发光性能,发现利用前者得到样品的发光不如后者的强,主要因为形成的基质网络结构不同。
采用sol-gel法制备了核壳结构分别为SiO2：Tb3+包覆SiO2颗粒(Si@Si-Tb)和SiO2包覆SiO2：Tb3+颗粒(Si-Tb@Si)两种结构,通过改变纳米材料的结构使得样品发光效率增大。在一定条件下核壳结构的发光强度较粉末SiO2：Tb3+的强,且得出0.8 Si@Si-Tb-z样品发光效率最高,即核质量为0.8g的SiO2颗粒分散在25ml的SiO2：Tb3+溶液,未经陈化得到的样品发光效率高。随着核质量的增加,发光离子数也增加,发光增强,但增加到一定值时,发光减弱。通过分析过滤后所得澄清溶液和沉淀所得样品的发光性能,发现上清液所得产物均比下层沉淀的发光强,而与核质量或结构无关。
SiO2 nano-meter luminescent materials with different types of doping or of different structure were prepared by the sol-gel and hydrothermal methods. The samples were characterized by Fluorescence Spectrum (PL), Fourier Transform Infrared Spectroscopy (FT-IR), Atomic Force Microscope (AFM) and Transmission Electron Microscope (TEM). And the luminous mechanism was studied in this paper.
Through the research of different factors such as the molar ratio of H2O and annealing temperature to the fluorescence, phosphorescence intensity and phosphorescence lifetime of the sample, it showed that all the factors had influence on the luminous intensity of Tb3+doped SiO2 xerogels or films, and resulted a competitive mechanism. With the increasing amount of water, the luminous intensity of the samples annealed at 750℃first weakened, then enhanced and last weakened again. Through analyzing the phosphor properties of the samples, we found that the variation curves of the phosphorescence and luminescence intensity vs. the molar ratio of H2O showed the same trend. And the molar ratio of H2O also largely affects the decay time of the phosphorescence. Additionally, the optimum mole ratio of TEOS:ETOH:H2O is set as 1:4:4. The aging last one day, and the optimum annealing temperature at which the luminescent intensity of SiO2:Re3+samples are strongest existed in the extent from 650 to 800℃.
SiO2:Re3+ luminescent xerogels and films doped Zn2+, Sn2+, Al3+ and other metal ions were prepared respectively by the sol-gel method, and the films were coated on the aerogel glasses or Si chips. The luminescent property of different metal ions doped SiO2:Re3+ samples with different forms were analyzed by making full use of the F-7000 fluorescence spectrometer. It was expected that the addition of metal ions can change the microcosmic environment of sample, as a result, the luminous efficiency of SiO2:Re3+, Mn+ would increase. Under the same conditions, the powder performed the strongest luminous intensity, followed by the film coated on glass as and Si substrate in turn. Due to the effect of local field increasing or energy transfer, the luminescent intensity of the metal ions doped SiO2:Re3+ samples were stronger than that of non-doped SiO2:Re3+ sample; the optimum annealing temperature also became lower; it corresponded to the different optimal concentrations of doped metal ions when the samples emitted the strongest light respectively, such as 0.4% for Zn2+, and 0.2% for Sn2+. In addition, the luminous intensity of the sample of SiO2:Tb3+, Zn2+ prepared through the hydrothermal method is weaker than that of the sample prepared by sol-gel preparation, mainly because of different formation of matrix network.
In order to increase the luminous efficiency of rare earth doped SiO2 samples by changing the structure of nano-materials, two kinds of core-shell structures were introduced, including SiO2:Tb3+ coated SiO2 nano-spheres particles (Si@Si-Tb) and SiO2 coated SiO2:Tb3+ nano-spheres particles (Si-Tb@Si). Under a certain condition, the luminous intensity of core-shell structure was stronger than that of the powders, conclusively, the 0.8Si@Si-Tb-z sample reached the highest luminous intensity, which means that the production obtained from SiO2 nano-spheres with 0.8g nuclear quality scattering in the 25ml SiO2:Tb3+ solution without aging had a higher luminous efficiency. With the increasing of nuclear quality, numbers of ions also increased, leading to higher luminous intensity. However, the light began abating when the nuclear quality increased to a certain value, probably because the concentration quenching effect of the luminous ions happened. Through the analyzing the luminous property of the clarifying solution and the deposition samples after filtering, it showed that the luminous intensity of the products of the upper clarify solution are stronger than that of the precipitation no matter how much nuclear quality.
通过研究不同含水量、退火温度等因素对样品的荧光强度,磷光强度和发光寿命等性能的影响,得知无论对于粉末还是薄膜形态的Tb3+掺杂SiO2发光材料,这些因素同时影响着Tb3+的发光性能,且对发光强度的影响形成了一个竞争机制。经750℃退火处理样品的发光强度,随含水量的增加,先减弱后增强之后又减弱。通过分析样品的磷光特性,得知含水量对磷光与荧光强度的变化趋势一致,且对发光衰减时间也有明显的影响。最终,确定正硅酸乙酯,无水乙醇和蒸馏水的最优摩尔比为1：4：4,陈化时间为一天,在650-800℃存在最佳退火温度使得样品SiO2：Re3+发光最强。
采用sol-gel法分别制备了Zn2+、Sn2+和Al3+等金属离子掺杂的SiO2：Re3+发光干凝胶和薄膜,薄膜分别镀在玻璃片和硅片上。充分利用F-7000荧光光谱仪分析了不同金属离子掺杂SiO2：Re3+样品的发光性能。通过掺杂金属离子改变稀土离子的微观环境使得样品SiO2：Re3+,Mn+发光效率增大。同等条件下,粉末发光最强,玻璃上镀的薄膜发光强度次之,硅片上镀的薄膜发光最弱。由于局域场增强或能量转移效应,金属离子掺杂SiO2：Re3+样品发光较不掺杂的强；金属离子掺杂样品所需的最佳退火温度比无掺杂样品的有所降低；不同类型金属离子掺杂SiO2：Re3+样品发光最强时对应的最佳浓度不同,如当Re是Tb时,Zn2+掺杂的最佳浓度为0.4%,而Sn2+为0.2%。此外,比较了利用水热法和溶胶凝胶法制备得到SiO2：Tb3+,Zn2+样品的发光性能,发现利用前者得到样品的发光不如后者的强,主要因为形成的基质网络结构不同。
采用sol-gel法制备了核壳结构分别为SiO2：Tb3+包覆SiO2颗粒(Si@Si-Tb)和SiO2包覆SiO2：Tb3+颗粒(Si-Tb@Si)两种结构,通过改变纳米材料的结构使得样品发光效率增大。在一定条件下核壳结构的发光强度较粉末SiO2：Tb3+的强,且得出0.8 Si@Si-Tb-z样品发光效率最高,即核质量为0.8g的SiO2颗粒分散在25ml的SiO2：Tb3+溶液,未经陈化得到的样品发光效率高。随着核质量的增加,发光离子数也增加,发光增强,但增加到一定值时,发光减弱。通过分析过滤后所得澄清溶液和沉淀所得样品的发光性能,发现上清液所得产物均比下层沉淀的发光强,而与核质量或结构无关。
SiO2 nano-meter luminescent materials with different types of doping or of different structure were prepared by the sol-gel and hydrothermal methods. The samples were characterized by Fluorescence Spectrum (PL), Fourier Transform Infrared Spectroscopy (FT-IR), Atomic Force Microscope (AFM) and Transmission Electron Microscope (TEM). And the luminous mechanism was studied in this paper.
Through the research of different factors such as the molar ratio of H2O and annealing temperature to the fluorescence, phosphorescence intensity and phosphorescence lifetime of the sample, it showed that all the factors had influence on the luminous intensity of Tb3+doped SiO2 xerogels or films, and resulted a competitive mechanism. With the increasing amount of water, the luminous intensity of the samples annealed at 750℃first weakened, then enhanced and last weakened again. Through analyzing the phosphor properties of the samples, we found that the variation curves of the phosphorescence and luminescence intensity vs. the molar ratio of H2O showed the same trend. And the molar ratio of H2O also largely affects the decay time of the phosphorescence. Additionally, the optimum mole ratio of TEOS:ETOH:H2O is set as 1:4:4. The aging last one day, and the optimum annealing temperature at which the luminescent intensity of SiO2:Re3+samples are strongest existed in the extent from 650 to 800℃.
SiO2:Re3+ luminescent xerogels and films doped Zn2+, Sn2+, Al3+ and other metal ions were prepared respectively by the sol-gel method, and the films were coated on the aerogel glasses or Si chips. The luminescent property of different metal ions doped SiO2:Re3+ samples with different forms were analyzed by making full use of the F-7000 fluorescence spectrometer. It was expected that the addition of metal ions can change the microcosmic environment of sample, as a result, the luminous efficiency of SiO2:Re3+, Mn+ would increase. Under the same conditions, the powder performed the strongest luminous intensity, followed by the film coated on glass as and Si substrate in turn. Due to the effect of local field increasing or energy transfer, the luminescent intensity of the metal ions doped SiO2:Re3+ samples were stronger than that of non-doped SiO2:Re3+ sample; the optimum annealing temperature also became lower; it corresponded to the different optimal concentrations of doped metal ions when the samples emitted the strongest light respectively, such as 0.4% for Zn2+, and 0.2% for Sn2+. In addition, the luminous intensity of the sample of SiO2:Tb3+, Zn2+ prepared through the hydrothermal method is weaker than that of the sample prepared by sol-gel preparation, mainly because of different formation of matrix network.
In order to increase the luminous efficiency of rare earth doped SiO2 samples by changing the structure of nano-materials, two kinds of core-shell structures were introduced, including SiO2:Tb3+ coated SiO2 nano-spheres particles (Si@Si-Tb) and SiO2 coated SiO2:Tb3+ nano-spheres particles (Si-Tb@Si). Under a certain condition, the luminous intensity of core-shell structure was stronger than that of the powders, conclusively, the 0.8Si@Si-Tb-z sample reached the highest luminous intensity, which means that the production obtained from SiO2 nano-spheres with 0.8g nuclear quality scattering in the 25ml SiO2:Tb3+ solution without aging had a higher luminous efficiency. With the increasing of nuclear quality, numbers of ions also increased, leading to higher luminous intensity. However, the light began abating when the nuclear quality increased to a certain value, probably because the concentration quenching effect of the luminous ions happened. Through the analyzing the luminous property of the clarifying solution and the deposition samples after filtering, it showed that the luminous intensity of the products of the upper clarify solution are stronger than that of the precipitation no matter how much nuclear quality.
引文
[1]白春礼.纳米科技及其发展前景[J].科学通报,2001,46(2)：89-91
[2]Zhu Chaofeng, Liang Xiaoluan, Yunxia Yang, et al. Luminescence properties of Tb doped and Tm/Tb/Sm co-doped glasses for LED applications [J]. Journal of Luminescence,2010, 130:74-77
[3]王桂珍.染料掺杂SiO2凝胶复合体系光学性质研究[D].济宁市：曲阜师范大学,2003
[4]姜建华.无机非金属材料工艺原理[M].北京：化学工业出版社,2005：522-536
[5]李建宇.稀土发光材料及其应用[M].北京：化学工业出版社,2003：1-16
[6]Hao Jianhua. Blue-light emission from Undoped and rare earth-doped wide Bandgap oxides [J]. Journal of Rare Earths,2006,24:728-731
[7]胡晓云,樊君,白晋涛,等.硼离子对Eu掺杂Si02干凝胶发光性能的影响[J].中国稀土学报,2005,23(6)：695-699
[8]Hu Xiaoyun, Fan Jun, Li Ting, et al. Novel trichromatic phosphor Co-doped with Eu, Tb in SiO2 gel matrix [J]. Chinese Science Bulletin,2007,52:444-449
[9]Hu Xiaoyun, Fan Jun, Zhang Dekai, et al. Tricolor white emitting phosphor co-doped with Eu, Dy in SiO2 matrix [J]. Chinese Science Bulletin,2008,53(22):3491-3496
[10]江东,胡晓云,苗仲海,等.纳米Si02基质中Eu3+的发光特性[J].中国激光,2009,36(2)：449-452
[11]Hu Xiaoyun, Fan Jun, Li Ting, et al. Preparation and luminescence properties of Eu2+ in SiO2 xerogels [J]. Opt. Mater.,2007,29:1327-1331
[12]胡晓云,曹大刚,李婷.纳米多孔Ti02薄膜制备工艺对其光学性能的影响[J].西北大学学报(自然科学版),2006,2,36(1)：50-54
[13]Sirimannea P M., Cheng Yi-Bing. Influence of some selected organic molecules on intensity of luminescence of TiO2:Eu3+ electrodes [J]. Journal of luminescence,2009,129 (5):563-565
[14]张锦,溶胶.凝胶法制备稀土掺杂二氧化钛基质纳米发光材料的研究[D].西安：西北大学,2007
[15]Magdalena Zalewska, Andrzej M. Klonkowski. Energy transfer from TiO2 nanocrystals to Tb3+ ions incorporated into silica [J].Optical Materials,2008,30(5):725-729
[16]Zhang Junying, Feng Haibing, Hao Weichang, et al. Luminescent properties of ZnO sol and film doped with Tb3+ ion. Materials Science and Engineering:A,2006,
425(1-2):346-348
[17]Zhong Mingya, Shan Guiye, Li Yajun. Synthesis and luminescence properties of Eu3+-doped ZnO nanocrystals by a hydrothermal process [J]. Materials Chemistry and Physics,2007,106(2-3):305-309
[18]Jong Su Kim, Ho Eun Kim, Ae Kyung Kwon, et al. Effect of initial pH on nanophosphor β-Ga2O3:Eu3+ prepared through sol-gel process [J]. Journal of Luminescence,2007, 122-123:710-713
[19]Elhouichet H., Othman L., Moadhen A. Enhanced photoluminescence of Tb3+ and Eu3+ induced by energy transfer from SnO2 and Si Nanocrystallines [J].2003, Materials Science and Engineering B,105:8-11
[20]Zhang Hongwu, Fu Xiaoyan, Niu Shuyun. Luminescence properties of Li+ doped nanosized SnO2:Eu [J]. Journal of Luminescence,2005,115, (1-2):7-12
[21]Lange S., Kiisk V., Reedo V. Luminescence of RE-ions in HfO2 thin films and some possible applications [J]. Optical Materials,2006,28(11):1238-1242
[22]莎仁,李霞,王喜贵.Zr02：Tb3+纳米晶的离子交换法制备及其发光特性[J].无机化学学报,2009,25(5)：844-848
[23]Guo Hai, Qiao Yanmin. Preparation, structural and photoluminescent properties of CeO2: Eu3+ films derived by Pechini sol-gel process [J]. Applied Surface Science,2008, 254(7):1961-1965
[24]Fan Guodong, Feng Changgen, Zhang Zhao. Surface and texture properties of Tb-doped deria-zirconia solid solution prepared by sol-gel method [J]. Journal of Rare Earths, Volume 25, Issue 1, February 2007, Pages 42-47
[25]A. Garcia Murillo, A. de J. Morales Ramirez, F. de J. Carrillo Romo, et al. Synthesis, structural and optical studies of sol-gel Gd2O3:Eu3+, Tb3+ films [J]. Materials Letters, 2009,63(18-19):1631-1634
[26]李秀明,吕树臣,刘金霞.纳米晶Zr02：Eu3+的制备及发光性质[J].发光学报,2005,(2)：220-224
[27]夏艳,王军转,石卓琼等.掺Er-Hf02薄膜材料的光致发光性质[J].半导体学报,2007,28(9)：1388-1391
[28]张中太,张俊英.无机光致发光材料及应用[M].北京：化学工业出版社,2005：126-157
[29]徐叙瑢,苏勉曾.发光学与发光材料[M].北京：化学工业出版社,2004：614-623
[30]江东.二氧化硅稀土发光材料的制备及性能研究[D].西安：西北大学,2009
[31]刘维红.稀土掺杂SiO2凝胶基质发光材料的制备及特性研究[D].西安：西北大学,2007
[32]苗仲海.溶胶-凝胶法制备Tb3-掺杂SiO2光致发光薄膜和电致发光薄膜研究[D].西安：西北大学,2008
[33]Lipowska Beata, Klonkowski Andrzej M. Energy transfer and surface plasmon resonance in luminescent materials based on Tb (Ⅲ) and Ag or Au nanoparticles in silica xerogel [J]. Journal of Non-Crystalline Solids,2008,354(35-39):4383-4387
[34]Hayakawa T., Selvan S.T., Nogami M. Field enhancement effect of small Ag particles on the fluorescence from Eu3+ doped SiO2 glass [J]. Apply Physics Letter,1999, 74:1513-1514
[35]C.Strohhofer, A.Polman. Silver as a sensitizer for erbium [J]. Appl. Phy. Lett.,2002, 81:1414-1416
[36]Armellini C., Ferrari M., Montagna M., et al. Terbium (Ⅲ) doped silica-xerogels:effect of aluminum (Ⅲ) co-doping [J]. Journal of Non-Crystalline Solids,1999,245(1-3): 115-121
[37]Zawadzki M., Hreniak D., Wrzyszcz J., et al. Photoluminescence and cathodoluminescence of Tb-doped Al2O3-ZrO2 nanostructures obtained by sol-gelmethod[J]. Chemical Physics,2003,291(3):275-285
[38]Dhlamini M.S., Ntwaeaborwa O.M., Swart H.C., et al. Sensitized luminescence through nanoscopic effects of ZnO encapsulated in SiO2:Tb3+ sol gel derived phosphor [J]. Physica B,2009,404:4406-4410
[39]Ntwaeaborwa O.M., Swart H.C., Kroon R.E.,et al. Enhanced luminescence and degradation of SiO2:Ce, Tb powder phosphors prepared by a sol-gel process[J]. Journal of Physics and Chemistry of Solids,2006,67(8):1749-1753
[40]毛艳丽,潘新华,林丙臣.K+和Al3+掺杂对掺Er3+溶胶凝胶玻璃发光特性的影响[J].光谱学与光谱分析,2007,27(7)：1283-1286
[41]Jia Changwen, Xie Erqing, Peng Aihua, et al. Photoluminescence and energy transfer of terbium doped titania film [J]. Thin Solid Films,2006,496:555-559
[42]华瑞年,田跃.ZnS:Tb/SiO2核壳结构纳米晶的光学性质[J].大连民族学院学报,2008,10,(1)：6-9
[43]Yang H., Holloway P. H. Enhance Photolum inescence from CdS:Mn/ZnS Core/shell Quantum Dots [J]. Appl. Phys. Lett.,2003,82 (12):1965-1967
[44]王忠志,陈向群,沈雷军.SiO2包覆Gd203:Er3+, Yb3+纳米粉的制备、结构及发光
性能[J].中国稀土学报,2009,27(3)：390-394
[45]李光植.铕、铽离子掺杂的核-壳结构发光材料的制备及发光性能研究[D].长春：东北师范大学,2007
[46]Wang Ying, Tang Zhi-yong, Liang Xiao-rong, et al. SiO2-coated CdTe nanowires: bristled nano centipedes [J]. Nano Lett,2004,4(2):225-231
[47]Okur S., Yakuphanoglu F., Stathatos E. High-mobility pentacene phototransistor with nanostructured SiO2 gate dielectric synthesized by sol-gel method [J]. Microelectronic Engineering,2010,87(4):635-640
[48]Yang Heqing, Yao Xi, Wang Xingjun, et al. Visible room-temperature photoluminescence of Ge-doped SiO2 glasses fabricated by a sol-gel process[J]. Optical Materials,2007, 29(6):631-635
[49]Kim J H, Jeon K A, Lee S Y. Formation Mechanism and Optical Properties of Nanocrystalline Silicon in Silicon Oxide [J]. J. Appl. Phys.,2005,98:014303.
[50]Ma Z Y, Chen K J, Huang X F, et al. Strong Blue Photoluminescence from As-fabricated Amorphous-Si:H/SiO2 Multilayers [J]. Appl. Phys. Lett.,2004,85(4):516-518
[51]宋春风,杨萍,吕孟凯,等.制备工艺条件对SiO2干凝胶发光性质的影响[J].硅酸盐通报,2003,2：89-92
[52]Pei Ling, Li Meiya, Liu Jun, Yu Benfang, et al. Improvements of the ferroelectric properties of high-valence Tb-doped Bi4Ti3O12 thin film grown by sol-gel method [J]. Materials Letters,2010,64(3):364-366
[53]王喜贵,李霞.Tb3+和Na2WO4共掺杂Si02材料的制备及其发光性质[J].光谱学与光谱分析,2008,28(2)：260-264
[54]M. Zawadzki, D. Hreniak, J. Wrzyszcz, et al. Photoluminescence and cathodoluminescence of Tb-doped Al2O3-ZrO2 nanostructures obtained by sol-gelmethod [J]. Chemical Physics,2003,291(3):275-285
[55]胡晓云.稀土掺杂凝胶基质发光材料的制备及性能研究[D].西安：西北大学,2005
[56]徐叙瑢,苏勉曾.发光学与发光材料[M].北京：化学工业出版社,2004：109-112
[57]郑子樵,李红英.稀土功能材料[M].北京：化学工业出版社,2003：170-172
[58]胡翔,李东升,程培红,等.表面等离激元对氮化硅薄膜中Tb3+离子荧光寿命的影响[J].发光学报,2008,29(4)：684-689
[59]Psuja P., Hreniak D., and Strek W. Rare-Earth Doped Nanocrystalline Phosphors for Field Emission Displays [J]. Journal of Nanomaterials,2007,2007:81350-1-81350-7
[60]Vedda, N. Chiodini, D. Di Martino, et al. Luminescence properties of rare-earth ions in SiO2 glasses prepared by the sol-gel method [J]. Journal of Non-Crystalline Solids,2004, 345-346:338-342
[61]Kazuhiko Tonooka, Katsuyoshi Shimokawa and Okio Nishimura.O.M. Ntwaeaborwa, et al. Preparation and luminescent properties of sol-gel derived SiO2-B2O3:Tb glass films [J]. Solid State Ionics,2002,151(1-4):105-110
[62]Bredol, M., Gutzov, S. Effect of germanium-codoping on the luminescence of terbium doped silica xerogels [J].Optical Materials,2002,20(3):233-239
[63]Zhong Huicai, Cai Weiping, Zhang Lide. Fluorescence properties of Tb3+ ions in SiO2 glass codoped with Al3+[J]. Materials Research Bulletin,1999,34(2):233-238
[64]Liu Xue-Jian, Li Hui-Li, Xie Rong-Jun, et al. Spectroscopic properties of nano-sized cerium-doped lutetium aluminum garnet phosphors via sol-gel combustion process [J]. Journal of Luminescence,2007,124(1):75-80
[65]Jin T., Tsutsumi S., Deguchi Y., et al. Preparation and luminescence characteristics of the europium and terbium complexes incorporated into a silica matrix using a sol-gel method [J]. Journal of Alloys and Compounds,1997,252:59-66
[66]Mauro Fasoli, Federico Moretti, Alessandro Lauria, et al. Radio-luminescence efficiency and rare-earth dispersion in Tb-doped silica glasses [J].Radiation Measurements,2007, 42(4-5):784-787
[67]王喜贵,于振友,娜米拉,等.Tb3+和Ga3+共掺杂的SiO2发光材料的制备、表征及发光性质的研究[J].内蒙古师范大学学报(自然科学汉文版),2008,37(2)：224-229
[68]石涛,周箭,申乾宏,等.溶胶-凝胶法制备纳米晶γ-Al2O3：Tb3+粉末及其发光性能[J].硅酸盐通报,2009,28(2)：224-228
[69]Brovelli S., Chiodini N., Meinardi F., et al. Confined diffusion of erbium excitations in SnO2 nanoparticles embedded in silica:A time-resolved infrared luminescence study [J]. Physical Review B,2009,79:153108-1-153108-4
[70]于立新,宋宏伟,刘钟馨,等.LaPO4:Ce3+/Tb3+纳米线的合成和发光特性[J].发光学报,2005,26(3)：369-373
[71]张茂峰,孟建新,刘应亮,等.水热法制备LaF3:Ce,Tb纳米荧光粉及发光性质研究[J].光谱学与光谱分析,2007,27(2)：222-235
[72]Carotta M.C., Gherardi S., MalaguC.,et al. Comparison between titania thick films obtained through sol-gel and hydrothermal synthetic processes [J]. Thin Solid Films,2007, 515:8339-8344
[73]Zhang Q.Y., Huang X.Y. Recent progress in quantum cutting phosphors [J]. Progress in Materials Science,2010,55:353-427.
[74]Leroy C., Cardinal T., Jubera V., et al. Sol-gel technique for the generation of europium-doped mesoporous and dense thin films:A luminescent study [J]. Journal of Luminescence,2009,129:1641-1645
[75]Omkaram I., Rao B.V., Buddhudu S. Effect of local environment and Sm3+-codoping on the luminescence properties in the Eu3+-doped potassium tungstate phosphor for white LEDs [J]. Journal of Alloys and Compounds,2009,474:565-568
[76]Fu Jiapeng, Zhang Qinghong, Li Yaogang, et al. Highly luminescent red light phosphor CaTiO3:Eu3+ under near-ultraviolet excitation[J]. Journal of Luminescence,2010, 130:231-235
[77]Fu Zuoling, Yang Hyun Kyoung, Moon Byung Kee, et al. Synthesis and luminescent properties of europium-activated Ca2SnO4phosphors by sol-gel method[J]. Journal of Luminescence,2009,129:1669-1672
[78]A. de J. Morales Rami'rez, A. Garci'a Murillo, F. de J. Carrillo Romo, et al. Properties of Gd2O3:Eu3+, Tb3+ nanopowders obtained by sol-gel process [J]. Materials Research Bulletin,2010,45:40-45
[79]Li Hong-Yan, Wu Jing, Huang Wei, et al. Synthesis and photoluminescent properties of five homodinuclear lanthanide (Ln3+= Eu3+, Sm3+, Er3+, Yb3+, Pr3+) complexes [J] Journal of Photochemistry and Photobiology A:Chemistry,2009,208:110-116
[80]Hoang-Duy Nguyen, Sun-il Mho, In-Hyeong Yeo. Preparation and characterization of nanosized (Y, Bi) VO4:Eu3+and Y (V, P) O4:Eu3+ red phosphors [J]. Journal of Luminescence,2009,129:1754-1758
[81]Afify N. D. and Mountjoy G. Molecular-dynamics modeling of Eu3+ ion clustering in SiO2 glass [J]. Physical Review B,2009, (79):024202-1-024202-12
[82]Yu Lixin, Masayuki Nogami.Upconversion luminescence properties of europium in ZnO-SiO2 glasses by femtosecond laser excitation [J]. Mater. Chem. Phys.,2008, 107:186-188
[83]Tomokatsu Hayakawa, Masayuki Nogami. High luminescence quantum efficiency of Eu3+ doped SnO2-SiO2 glasses due to excitation energy transfer from nano-sized SnO2 crystals [J]. Science and Technology of Advanced Materials,2005,6(1):66-70
[84]Yu Yunlong, Chen Daqin, Huang Ping, et al. Structure and luminescence of Eu3+ doped glass ceramics embedding ZnO quantum dots [J].2010,36(3):1091-1094
[85]Sung-Sik Chang,Dong Kee Park.Novel Sn powder preparation by spark processing and luminescence properties[J]. Materials Science and Engineering B,2002,95:55-60
[86]Andrea Cannizzo,Maurizio Leone,Roberto Boscaino,et al. Luminescence and absorption spectroscopy of Sn-related impurity centers in silica[J] Journal of Non-Crystalline Solids, 2006,352:2082-2089
[87]华瑞年,田跃.ZnS:Tb/SiO2核壳结构纳米晶的光学性质[J].大连民族学院学报,2008,10,(1)：6-9
[88]Yang H., Holloway P. H. Enhance Photolum inescence from CdS:Mn/ZnS Core/shell Quantum Dots [J]. Appl. Phys. Lett.,2003,82 (12):1965-1967
[89]王忠志,陈向群,沈雷军.Si02包覆Gd203:Er3+, yb3+纳米粉的制备、结构及发光性能[J].中国稀土学报,2009,27(3)：390-394
[90]李光植.铕、铽离子掺杂的核-壳结构发光材料的制备及发光性能研究[D].长春：东北师范大学,2007
[2]Zhu Chaofeng, Liang Xiaoluan, Yunxia Yang, et al. Luminescence properties of Tb doped and Tm/Tb/Sm co-doped glasses for LED applications [J]. Journal of Luminescence,2010, 130:74-77
[3]王桂珍.染料掺杂SiO2凝胶复合体系光学性质研究[D].济宁市：曲阜师范大学,2003
[4]姜建华.无机非金属材料工艺原理[M].北京：化学工业出版社,2005：522-536
[5]李建宇.稀土发光材料及其应用[M].北京：化学工业出版社,2003：1-16
[6]Hao Jianhua. Blue-light emission from Undoped and rare earth-doped wide Bandgap oxides [J]. Journal of Rare Earths,2006,24:728-731
[7]胡晓云,樊君,白晋涛,等.硼离子对Eu掺杂Si02干凝胶发光性能的影响[J].中国稀土学报,2005,23(6)：695-699
[8]Hu Xiaoyun, Fan Jun, Li Ting, et al. Novel trichromatic phosphor Co-doped with Eu, Tb in SiO2 gel matrix [J]. Chinese Science Bulletin,2007,52:444-449
[9]Hu Xiaoyun, Fan Jun, Zhang Dekai, et al. Tricolor white emitting phosphor co-doped with Eu, Dy in SiO2 matrix [J]. Chinese Science Bulletin,2008,53(22):3491-3496
[10]江东,胡晓云,苗仲海,等.纳米Si02基质中Eu3+的发光特性[J].中国激光,2009,36(2)：449-452
[11]Hu Xiaoyun, Fan Jun, Li Ting, et al. Preparation and luminescence properties of Eu2+ in SiO2 xerogels [J]. Opt. Mater.,2007,29:1327-1331
[12]胡晓云,曹大刚,李婷.纳米多孔Ti02薄膜制备工艺对其光学性能的影响[J].西北大学学报(自然科学版),2006,2,36(1)：50-54
[13]Sirimannea P M., Cheng Yi-Bing. Influence of some selected organic molecules on intensity of luminescence of TiO2:Eu3+ electrodes [J]. Journal of luminescence,2009,129 (5):563-565
[14]张锦,溶胶.凝胶法制备稀土掺杂二氧化钛基质纳米发光材料的研究[D].西安：西北大学,2007
[15]Magdalena Zalewska, Andrzej M. Klonkowski. Energy transfer from TiO2 nanocrystals to Tb3+ ions incorporated into silica [J].Optical Materials,2008,30(5):725-729
[16]Zhang Junying, Feng Haibing, Hao Weichang, et al. Luminescent properties of ZnO sol and film doped with Tb3+ ion. Materials Science and Engineering:A,2006,
425(1-2):346-348
[17]Zhong Mingya, Shan Guiye, Li Yajun. Synthesis and luminescence properties of Eu3+-doped ZnO nanocrystals by a hydrothermal process [J]. Materials Chemistry and Physics,2007,106(2-3):305-309
[18]Jong Su Kim, Ho Eun Kim, Ae Kyung Kwon, et al. Effect of initial pH on nanophosphor β-Ga2O3:Eu3+ prepared through sol-gel process [J]. Journal of Luminescence,2007, 122-123:710-713
[19]Elhouichet H., Othman L., Moadhen A. Enhanced photoluminescence of Tb3+ and Eu3+ induced by energy transfer from SnO2 and Si Nanocrystallines [J].2003, Materials Science and Engineering B,105:8-11
[20]Zhang Hongwu, Fu Xiaoyan, Niu Shuyun. Luminescence properties of Li+ doped nanosized SnO2:Eu [J]. Journal of Luminescence,2005,115, (1-2):7-12
[21]Lange S., Kiisk V., Reedo V. Luminescence of RE-ions in HfO2 thin films and some possible applications [J]. Optical Materials,2006,28(11):1238-1242
[22]莎仁,李霞,王喜贵.Zr02：Tb3+纳米晶的离子交换法制备及其发光特性[J].无机化学学报,2009,25(5)：844-848
[23]Guo Hai, Qiao Yanmin. Preparation, structural and photoluminescent properties of CeO2: Eu3+ films derived by Pechini sol-gel process [J]. Applied Surface Science,2008, 254(7):1961-1965
[24]Fan Guodong, Feng Changgen, Zhang Zhao. Surface and texture properties of Tb-doped deria-zirconia solid solution prepared by sol-gel method [J]. Journal of Rare Earths, Volume 25, Issue 1, February 2007, Pages 42-47
[25]A. Garcia Murillo, A. de J. Morales Ramirez, F. de J. Carrillo Romo, et al. Synthesis, structural and optical studies of sol-gel Gd2O3:Eu3+, Tb3+ films [J]. Materials Letters, 2009,63(18-19):1631-1634
[26]李秀明,吕树臣,刘金霞.纳米晶Zr02：Eu3+的制备及发光性质[J].发光学报,2005,(2)：220-224
[27]夏艳,王军转,石卓琼等.掺Er-Hf02薄膜材料的光致发光性质[J].半导体学报,2007,28(9)：1388-1391
[28]张中太,张俊英.无机光致发光材料及应用[M].北京：化学工业出版社,2005：126-157
[29]徐叙瑢,苏勉曾.发光学与发光材料[M].北京：化学工业出版社,2004：614-623
[30]江东.二氧化硅稀土发光材料的制备及性能研究[D].西安：西北大学,2009
[31]刘维红.稀土掺杂SiO2凝胶基质发光材料的制备及特性研究[D].西安：西北大学,2007
[32]苗仲海.溶胶-凝胶法制备Tb3-掺杂SiO2光致发光薄膜和电致发光薄膜研究[D].西安：西北大学,2008
[33]Lipowska Beata, Klonkowski Andrzej M. Energy transfer and surface plasmon resonance in luminescent materials based on Tb (Ⅲ) and Ag or Au nanoparticles in silica xerogel [J]. Journal of Non-Crystalline Solids,2008,354(35-39):4383-4387
[34]Hayakawa T., Selvan S.T., Nogami M. Field enhancement effect of small Ag particles on the fluorescence from Eu3+ doped SiO2 glass [J]. Apply Physics Letter,1999, 74:1513-1514
[35]C.Strohhofer, A.Polman. Silver as a sensitizer for erbium [J]. Appl. Phy. Lett.,2002, 81:1414-1416
[36]Armellini C., Ferrari M., Montagna M., et al. Terbium (Ⅲ) doped silica-xerogels:effect of aluminum (Ⅲ) co-doping [J]. Journal of Non-Crystalline Solids,1999,245(1-3): 115-121
[37]Zawadzki M., Hreniak D., Wrzyszcz J., et al. Photoluminescence and cathodoluminescence of Tb-doped Al2O3-ZrO2 nanostructures obtained by sol-gelmethod[J]. Chemical Physics,2003,291(3):275-285
[38]Dhlamini M.S., Ntwaeaborwa O.M., Swart H.C., et al. Sensitized luminescence through nanoscopic effects of ZnO encapsulated in SiO2:Tb3+ sol gel derived phosphor [J]. Physica B,2009,404:4406-4410
[39]Ntwaeaborwa O.M., Swart H.C., Kroon R.E.,et al. Enhanced luminescence and degradation of SiO2:Ce, Tb powder phosphors prepared by a sol-gel process[J]. Journal of Physics and Chemistry of Solids,2006,67(8):1749-1753
[40]毛艳丽,潘新华,林丙臣.K+和Al3+掺杂对掺Er3+溶胶凝胶玻璃发光特性的影响[J].光谱学与光谱分析,2007,27(7)：1283-1286
[41]Jia Changwen, Xie Erqing, Peng Aihua, et al. Photoluminescence and energy transfer of terbium doped titania film [J]. Thin Solid Films,2006,496:555-559
[42]华瑞年,田跃.ZnS:Tb/SiO2核壳结构纳米晶的光学性质[J].大连民族学院学报,2008,10,(1)：6-9
[43]Yang H., Holloway P. H. Enhance Photolum inescence from CdS:Mn/ZnS Core/shell Quantum Dots [J]. Appl. Phys. Lett.,2003,82 (12):1965-1967
[44]王忠志,陈向群,沈雷军.SiO2包覆Gd203:Er3+, Yb3+纳米粉的制备、结构及发光
性能[J].中国稀土学报,2009,27(3)：390-394
[45]李光植.铕、铽离子掺杂的核-壳结构发光材料的制备及发光性能研究[D].长春：东北师范大学,2007
[46]Wang Ying, Tang Zhi-yong, Liang Xiao-rong, et al. SiO2-coated CdTe nanowires: bristled nano centipedes [J]. Nano Lett,2004,4(2):225-231
[47]Okur S., Yakuphanoglu F., Stathatos E. High-mobility pentacene phototransistor with nanostructured SiO2 gate dielectric synthesized by sol-gel method [J]. Microelectronic Engineering,2010,87(4):635-640
[48]Yang Heqing, Yao Xi, Wang Xingjun, et al. Visible room-temperature photoluminescence of Ge-doped SiO2 glasses fabricated by a sol-gel process[J]. Optical Materials,2007, 29(6):631-635
[49]Kim J H, Jeon K A, Lee S Y. Formation Mechanism and Optical Properties of Nanocrystalline Silicon in Silicon Oxide [J]. J. Appl. Phys.,2005,98:014303.
[50]Ma Z Y, Chen K J, Huang X F, et al. Strong Blue Photoluminescence from As-fabricated Amorphous-Si:H/SiO2 Multilayers [J]. Appl. Phys. Lett.,2004,85(4):516-518
[51]宋春风,杨萍,吕孟凯,等.制备工艺条件对SiO2干凝胶发光性质的影响[J].硅酸盐通报,2003,2：89-92
[52]Pei Ling, Li Meiya, Liu Jun, Yu Benfang, et al. Improvements of the ferroelectric properties of high-valence Tb-doped Bi4Ti3O12 thin film grown by sol-gel method [J]. Materials Letters,2010,64(3):364-366
[53]王喜贵,李霞.Tb3+和Na2WO4共掺杂Si02材料的制备及其发光性质[J].光谱学与光谱分析,2008,28(2)：260-264
[54]M. Zawadzki, D. Hreniak, J. Wrzyszcz, et al. Photoluminescence and cathodoluminescence of Tb-doped Al2O3-ZrO2 nanostructures obtained by sol-gelmethod [J]. Chemical Physics,2003,291(3):275-285
[55]胡晓云.稀土掺杂凝胶基质发光材料的制备及性能研究[D].西安：西北大学,2005
[56]徐叙瑢,苏勉曾.发光学与发光材料[M].北京：化学工业出版社,2004：109-112
[57]郑子樵,李红英.稀土功能材料[M].北京：化学工业出版社,2003：170-172
[58]胡翔,李东升,程培红,等.表面等离激元对氮化硅薄膜中Tb3+离子荧光寿命的影响[J].发光学报,2008,29(4)：684-689
[59]Psuja P., Hreniak D., and Strek W. Rare-Earth Doped Nanocrystalline Phosphors for Field Emission Displays [J]. Journal of Nanomaterials,2007,2007:81350-1-81350-7
[60]Vedda, N. Chiodini, D. Di Martino, et al. Luminescence properties of rare-earth ions in SiO2 glasses prepared by the sol-gel method [J]. Journal of Non-Crystalline Solids,2004, 345-346:338-342
[61]Kazuhiko Tonooka, Katsuyoshi Shimokawa and Okio Nishimura.O.M. Ntwaeaborwa, et al. Preparation and luminescent properties of sol-gel derived SiO2-B2O3:Tb glass films [J]. Solid State Ionics,2002,151(1-4):105-110
[62]Bredol, M., Gutzov, S. Effect of germanium-codoping on the luminescence of terbium doped silica xerogels [J].Optical Materials,2002,20(3):233-239
[63]Zhong Huicai, Cai Weiping, Zhang Lide. Fluorescence properties of Tb3+ ions in SiO2 glass codoped with Al3+[J]. Materials Research Bulletin,1999,34(2):233-238
[64]Liu Xue-Jian, Li Hui-Li, Xie Rong-Jun, et al. Spectroscopic properties of nano-sized cerium-doped lutetium aluminum garnet phosphors via sol-gel combustion process [J]. Journal of Luminescence,2007,124(1):75-80
[65]Jin T., Tsutsumi S., Deguchi Y., et al. Preparation and luminescence characteristics of the europium and terbium complexes incorporated into a silica matrix using a sol-gel method [J]. Journal of Alloys and Compounds,1997,252:59-66
[66]Mauro Fasoli, Federico Moretti, Alessandro Lauria, et al. Radio-luminescence efficiency and rare-earth dispersion in Tb-doped silica glasses [J].Radiation Measurements,2007, 42(4-5):784-787
[67]王喜贵,于振友,娜米拉,等.Tb3+和Ga3+共掺杂的SiO2发光材料的制备、表征及发光性质的研究[J].内蒙古师范大学学报(自然科学汉文版),2008,37(2)：224-229
[68]石涛,周箭,申乾宏,等.溶胶-凝胶法制备纳米晶γ-Al2O3：Tb3+粉末及其发光性能[J].硅酸盐通报,2009,28(2)：224-228
[69]Brovelli S., Chiodini N., Meinardi F., et al. Confined diffusion of erbium excitations in SnO2 nanoparticles embedded in silica:A time-resolved infrared luminescence study [J]. Physical Review B,2009,79:153108-1-153108-4
[70]于立新,宋宏伟,刘钟馨,等.LaPO4:Ce3+/Tb3+纳米线的合成和发光特性[J].发光学报,2005,26(3)：369-373
[71]张茂峰,孟建新,刘应亮,等.水热法制备LaF3:Ce,Tb纳米荧光粉及发光性质研究[J].光谱学与光谱分析,2007,27(2)：222-235
[72]Carotta M.C., Gherardi S., MalaguC.,et al. Comparison between titania thick films obtained through sol-gel and hydrothermal synthetic processes [J]. Thin Solid Films,2007, 515:8339-8344
[73]Zhang Q.Y., Huang X.Y. Recent progress in quantum cutting phosphors [J]. Progress in Materials Science,2010,55:353-427.
[74]Leroy C., Cardinal T., Jubera V., et al. Sol-gel technique for the generation of europium-doped mesoporous and dense thin films:A luminescent study [J]. Journal of Luminescence,2009,129:1641-1645
[75]Omkaram I., Rao B.V., Buddhudu S. Effect of local environment and Sm3+-codoping on the luminescence properties in the Eu3+-doped potassium tungstate phosphor for white LEDs [J]. Journal of Alloys and Compounds,2009,474:565-568
[76]Fu Jiapeng, Zhang Qinghong, Li Yaogang, et al. Highly luminescent red light phosphor CaTiO3:Eu3+ under near-ultraviolet excitation[J]. Journal of Luminescence,2010, 130:231-235
[77]Fu Zuoling, Yang Hyun Kyoung, Moon Byung Kee, et al. Synthesis and luminescent properties of europium-activated Ca2SnO4phosphors by sol-gel method[J]. Journal of Luminescence,2009,129:1669-1672
[78]A. de J. Morales Rami'rez, A. Garci'a Murillo, F. de J. Carrillo Romo, et al. Properties of Gd2O3:Eu3+, Tb3+ nanopowders obtained by sol-gel process [J]. Materials Research Bulletin,2010,45:40-45
[79]Li Hong-Yan, Wu Jing, Huang Wei, et al. Synthesis and photoluminescent properties of five homodinuclear lanthanide (Ln3+= Eu3+, Sm3+, Er3+, Yb3+, Pr3+) complexes [J] Journal of Photochemistry and Photobiology A:Chemistry,2009,208:110-116
[80]Hoang-Duy Nguyen, Sun-il Mho, In-Hyeong Yeo. Preparation and characterization of nanosized (Y, Bi) VO4:Eu3+and Y (V, P) O4:Eu3+ red phosphors [J]. Journal of Luminescence,2009,129:1754-1758
[81]Afify N. D. and Mountjoy G. Molecular-dynamics modeling of Eu3+ ion clustering in SiO2 glass [J]. Physical Review B,2009, (79):024202-1-024202-12
[82]Yu Lixin, Masayuki Nogami.Upconversion luminescence properties of europium in ZnO-SiO2 glasses by femtosecond laser excitation [J]. Mater. Chem. Phys.,2008, 107:186-188
[83]Tomokatsu Hayakawa, Masayuki Nogami. High luminescence quantum efficiency of Eu3+ doped SnO2-SiO2 glasses due to excitation energy transfer from nano-sized SnO2 crystals [J]. Science and Technology of Advanced Materials,2005,6(1):66-70
[84]Yu Yunlong, Chen Daqin, Huang Ping, et al. Structure and luminescence of Eu3+ doped glass ceramics embedding ZnO quantum dots [J].2010,36(3):1091-1094
[85]Sung-Sik Chang,Dong Kee Park.Novel Sn powder preparation by spark processing and luminescence properties[J]. Materials Science and Engineering B,2002,95:55-60
[86]Andrea Cannizzo,Maurizio Leone,Roberto Boscaino,et al. Luminescence and absorption spectroscopy of Sn-related impurity centers in silica[J] Journal of Non-Crystalline Solids, 2006,352:2082-2089
[87]华瑞年,田跃.ZnS:Tb/SiO2核壳结构纳米晶的光学性质[J].大连民族学院学报,2008,10,(1)：6-9
[88]Yang H., Holloway P. H. Enhance Photolum inescence from CdS:Mn/ZnS Core/shell Quantum Dots [J]. Appl. Phys. Lett.,2003,82 (12):1965-1967
[89]王忠志,陈向群,沈雷军.Si02包覆Gd203:Er3+, yb3+纳米粉的制备、结构及发光性能[J].中国稀土学报,2009,27(3)：390-394
[90]李光植.铕、铽离子掺杂的核-壳结构发光材料的制备及发光性能研究[D].长春：东北师范大学,2007