稀土掺杂的LaAlO_3/YAG的制备及其光谱性质的研究
摘要
稀土发光材料的应用一直是重点的高新技术领域,在照明、显示、信息传递等领域都有广泛的应用。上转换发光材料能够将红外光子转变成可见光,在医学探测上有广阔的应用前景,而量子剪裁发光材料能够将高能量的光子转变成两个或两个以上低能量的光子,提高能量利用效率
铝酸盐基质材料的化学性质稳定、抗热和抗机械力性能优秀,在紫外和真空紫外波段有很强的吸收,是一类广受重视的基质材料,并且在PDP显示领域和无汞荧光灯方面有广泛的应用。YAG是一种钙钛矿结构的铝酸盐,是一种好的激光和闪烁体基质,而与其结构相类似的LaAlO3被作为发光材料研究的报道却很少。
本论文主要做了以下工作：
1.采用共沉淀法制备了纳米LaAlO3基质,研究了不同反应条件对产物结晶性能与粒径的影响,X射线衍射图谱和SEM表明,升高温度和提高反应时间都可以使LaAlO3的结晶性能变好,但是升高温度会使其粒径变大,导致团聚。
2.研究了LaAlO3基质中Tb3+的发光性能,常温下光谱性质表明,当Tb3+的掺杂浓度小于1%时,5D3、5D4发光强度随浓度的增大而增强,当浓度达到1%时会发生浓度猝灭,5D3的发光强度会减小。升高温度和延长反应时间都可以使Tb3+的发光变强。
3.研究了LaAlO3基质中Tb3+、Yb3+离子之间的能量传递过程,结果表明以980nm激发样品时,会发生上转换发光,为双光子过程。在Tb3+、Gd3+共掺杂的基质中,观察到了Gd3+对Tb3+的能量传递,对Tb3+起到敏化作用。
4.制备并表征了YAG:Pr3+,Eu3+体系,对Pr3+,Eu3+之间的能量传递有了初步的认识。
The application of Rare Earth Luminescent Materials has been the focus in high-tech fields, such as lighting, display, messaging and so on. Upconversion luminescence materials can change infrared photons into visible light, while quantum cutting light materials can absorb high-energy photons and release double or more low-energy photons, so the former has a great prospect in bio-detection and the later may raise energy efficiency.
Aluminates substrate phosphors had attracted a lot of attention because of their excellent chemical, thermal stability and highly absorption of ultraviolet and vacuum ultraviolet photons. YAG, whose molecular formula is YAl5O12 has been a good laser and seintillator matrix, while LaAlO>3 has not received enough attention although its structure is similar to YAG.
The research include the following contents:
1. LaAlO3 matrix was prepared by co-precipitation method. The effect on the performance and size of crystals was studied in different reaction conditions. X-ray diffraction and SEM showed that higher temperature and longer reaction time would improve the crystallization properties of LaAlO3, but the higher temperature would increase the particle size, inducing reunion.
2. The luminescence properties of Tb3+doped in LaAlO3matrix has been studied. Spectral on room temperature showed that the luminescence intensity increased with increasing concentration when the Tb3+doping concentration was less than 1% and opposite when the concentration was more than 1%. Higher temperature and longer reaction time would enhance Tb3+luminescence intensity.
3. We studied the energy transfer between Tb3+ and Yb3+ ion in LaAlO3 matrix. When the samples was excited by light in 980nm the up-conversion process would occur, indicating the two-photon process. When the light was changed to 193nm, down-conversion would occur. The energy transfer from Gd3+ toTb3+ in matrix was observed, sensitizing Tb3+ions.
4. Preparation and Characterization of a YAG/Pr3+, Eu3+ system helped the understanding of the energy transfer between Pr3+ and Eu3+.
铝酸盐基质材料的化学性质稳定、抗热和抗机械力性能优秀,在紫外和真空紫外波段有很强的吸收,是一类广受重视的基质材料,并且在PDP显示领域和无汞荧光灯方面有广泛的应用。YAG是一种钙钛矿结构的铝酸盐,是一种好的激光和闪烁体基质,而与其结构相类似的LaAlO3被作为发光材料研究的报道却很少。
本论文主要做了以下工作：
1.采用共沉淀法制备了纳米LaAlO3基质,研究了不同反应条件对产物结晶性能与粒径的影响,X射线衍射图谱和SEM表明,升高温度和提高反应时间都可以使LaAlO3的结晶性能变好,但是升高温度会使其粒径变大,导致团聚。
2.研究了LaAlO3基质中Tb3+的发光性能,常温下光谱性质表明,当Tb3+的掺杂浓度小于1%时,5D3、5D4发光强度随浓度的增大而增强,当浓度达到1%时会发生浓度猝灭,5D3的发光强度会减小。升高温度和延长反应时间都可以使Tb3+的发光变强。
3.研究了LaAlO3基质中Tb3+、Yb3+离子之间的能量传递过程,结果表明以980nm激发样品时,会发生上转换发光,为双光子过程。在Tb3+、Gd3+共掺杂的基质中,观察到了Gd3+对Tb3+的能量传递,对Tb3+起到敏化作用。
4.制备并表征了YAG:Pr3+,Eu3+体系,对Pr3+,Eu3+之间的能量传递有了初步的认识。
The application of Rare Earth Luminescent Materials has been the focus in high-tech fields, such as lighting, display, messaging and so on. Upconversion luminescence materials can change infrared photons into visible light, while quantum cutting light materials can absorb high-energy photons and release double or more low-energy photons, so the former has a great prospect in bio-detection and the later may raise energy efficiency.
Aluminates substrate phosphors had attracted a lot of attention because of their excellent chemical, thermal stability and highly absorption of ultraviolet and vacuum ultraviolet photons. YAG, whose molecular formula is YAl5O12 has been a good laser and seintillator matrix, while LaAlO>3 has not received enough attention although its structure is similar to YAG.
The research include the following contents:
1. LaAlO3 matrix was prepared by co-precipitation method. The effect on the performance and size of crystals was studied in different reaction conditions. X-ray diffraction and SEM showed that higher temperature and longer reaction time would improve the crystallization properties of LaAlO3, but the higher temperature would increase the particle size, inducing reunion.
2. The luminescence properties of Tb3+doped in LaAlO3matrix has been studied. Spectral on room temperature showed that the luminescence intensity increased with increasing concentration when the Tb3+doping concentration was less than 1% and opposite when the concentration was more than 1%. Higher temperature and longer reaction time would enhance Tb3+luminescence intensity.
3. We studied the energy transfer between Tb3+ and Yb3+ ion in LaAlO3 matrix. When the samples was excited by light in 980nm the up-conversion process would occur, indicating the two-photon process. When the light was changed to 193nm, down-conversion would occur. The energy transfer from Gd3+ toTb3+ in matrix was observed, sensitizing Tb3+ions.
4. Preparation and Characterization of a YAG/Pr3+, Eu3+ system helped the understanding of the energy transfer between Pr3+ and Eu3+.
引文
[1]贡长生,张克立.新型功能材料[M].北京：化学工业出版社,2001.
[2]李颖,赵永亮.稀土材料在高科技领域中的应用[J].内蒙古石油化工,2005,31(5)：9-11.
[3]卢利平.稀土发光材料[M].北京：国防工业出版社,2005,10-15.
[4]郑子樵,李红英.稀土功能材料[M].北京：化学工业出版社,2003.
[5]刘小珍.稀土精细化学品化学[M].北京：化学工业出版社,2009,7.
[6]徐光宪.稀土[M].北京：冶金工业出版社.1995,133.
[7]李建宇.稀土发光材料及其应用[M].北京：化学工业出版社,2003..
[8]莎仁,王喜贵.纳米晶LaAlO3掺Eu3+的复合沉淀制备及其光学性质的研究[J].影像科学与光化学.2009：27(6),435-440.
[9]F.Auzel,Compat,Rend.Acad.Connection between ture effective mass and optical absorption in insulator,Sci.Paris.1959,2:84-88.
[10]Auzel.F. Pecile D.Morin D,J Electrochem soc,1975,122(1),101.
[11]陈小波,宋增福.Er,Yb氟氧化物玻璃陶瓷的上转换发光特征饱和现象综合分析[J].光谱学与光谱分析.2005：25(2),161-165.
[12]沈毅,王少艳.上转换发光材料研究进展与应用[J].河北理工大学学报.2009：31(1),76-77.
[13]朱立刚,肖卓豪,卢安贤.上转换发光氧氟微晶研究进展.材料导报[J].2009：23(3),41
[14]乌兰图亚.稀土离子上转换发光研究进展[J].内蒙古石油化工.2007(12),19.
[15]何捍卫等.红外-可见光的上转换材料研究进展.中国稀土学报.2003：21(2),21.
[16]聂秋华.蓝绿光上转换荧光输出的稀土掺杂玻璃研究进展,硅酸盐通报2006.10；25(5).
[17]Yang Kui Sheng,Li Yan,Yu Chao Yi.upconversion luminescence of Ho3+,Tm3+,Yb3+co-doped Nanocrystal NaYF4 synthesized by Hydrothermal method[J] Journal of rare earths.2006(24):757-760.
[18]Yang Wei,Feng Qi Lu,Xinrong Zhang.Poly-mediated synthesis and luminescence of lanthanide-doped NaYF4 Nanocrystal upconversion phosphors[J] Journal of Alloy and compounds 455(2008),376-384.
[19]陈宝玖,王海宁,秦伟平等.高效的红外到可见上转换氟氧化物玻璃材料[J].光谱学与光谱分析.2003,20(3)：257.
[20]Kaczkan M, Frukcuz Z,Malinowskim. Infrared to visible wavelength upconversion in Sm3+-actived YAG crystal[J]. Journal of Alloy and compounds.2001,323-324:736.
[21]Fan WH,Hon X,Zhao W,etal.Effect of the growth conditions on infrared upconversion efficiency of CaS:Eu,Sm thin films[J].APPL,Phys A.2001,73:115.
[22]R.T.Wegh.Hdnker,KD.oskam,A.Meijerink.J.Alloys Comps 2000;97-89,1017.
[23]H.Y.Tzeng,B.M.cheng.T.M.chen,J.Lumin,122,(2007)917.
[24]李岩.稀土离子掺杂的NaYF4上转换纳米晶的制备与表征[D].2006.1
[25]张吉林,洪广言.稀土纳米发光材料研究进展[J].发光学报.2005：26(3)286-287.
[26]G.M.Qiu, Y.B. Sun, S.Q. Zhang, M. Zhang, C.H. Yan, S.J. Dai. Preparation and structure characterization of rare earth doped Alumina-siloxane gel and its modification on Er effect. Journal Of Rare Earths,2004;2,15.
[27]Xiao zhi guo.Long after glow silicate luminescent material and its manufacturing method[P].usp6093346.
[28]徐叙熔,苏勉曾.发光学与发光材料[M].北京：化学工业出版社,2004.
[29]M.J.weber.Journal Of Luminescence[J].100(2002)35.
[30]应跟裕,胡文波,邱勇.平板显示技术[M].北京：人民邮电出版社,2002.
[31]刘行仁.白光LED现状和问题.光源与照明.2003,3：4-8.
[32]王晓明,郭伟玲,高国等.LED-新一代照明光源[J].现代显示.2005(53)：15-19.
[33]J.P.countures.The Al2O3-Nd2O3 phase Diagram[J]. Journal of the American ceramic society.1985(68):105-107.
[34]罗岚,徐政,刘庆峰等.GdA103:Eu3+荧光粉燃烧合成及其光学性能.同济大学学报.2004,32(11)：1476-1479.
[35]Smets BMJ,BerlijsdonkJ G,The luminescence properties of Eu3+ and Mn2+ doped barium hexoaluminates,Material Reserch Bullitin,1986,21:1305-1310.
[36]Liu J R,Song L. Highly power Nd: Y3AL5O12 ceramic laser. Jpn. J. Appl. Phys.2000; 39: 1048-50p.
[37]张慰萍.稀土掺杂的纳米发光材料的制备和发光[J].发光学报2000;4(21)：314-9p.
[38]Jun Zhou, Yuhua Wang, Bitao Liu. Effect of H3BO3 on structure and photoluminescence of BaAl12O19:Mn2+ phosphor under VUV excitation.2009 Sepl8th;484:439-43p.
[39]董岩,张超,蒋建清,梁步清,刘凯,于金.掺杂元素对BaAI12019:Mn2+荧光粉发光性能的影响.东南大学学报(自然科学版)2005;35(6)：911-4p.
[40]李晓云,陆长天,梁爽.铝酸锶系长余辉发光粉的制备及其光学性能.南京化工大学学报,2001;23(2),32—35.
[41]袁鹏,李保平,王介强.微波均相沉淀法合成纳米粉体的研究进展.中国粉体技术2008.14.2.
[42]L. E. Shea. Synthesis of red-emitting, small particle size luminescent oxides using an optimize combustion process [J]. Journal of the American Ceramic Society 1996,79(32):57-61.
[43]S. Ekambaram, M. Maaza. Combustion synthesis and luminescent properties of Eu3+ activated cheap red phosphors [J]. J. Alloys Comps 2005; 395(1-2):132-4p.
[44]张世英,李德意,魏坤.溶胶凝胶法制备BaMgAl10O17:EU荧光粉的研究.中国陶瓷工业 2003;10(2):36—38p.
[45]Raviehandran D, Roy R, White W B. Synlhesis and Characterization of Sol-Gel Derived Hexa-Aluminate Phosphors[J]. Journal of Material Research 1997,12(3):819.
[46]R P. Rao. Tm3+ activated lanthanum phosphate: a blue PDP phosphor [J]. Journal of Luminescence 2005,113(3-4):271-8p.
[47]赵春燕,朱连杰,冯守华.BaBeF4:Sm3+的温和水热合成与光谱性质研究[J].高等学校化学学报,1998,19(7)：1023-25.
[48]陈江.Tb3+自敏化效应与Gd3+-Tb3+能量转移对硅酸盐玻璃发光性能的影响[J].玻璃与搪瓷.2009;37.3.
[49]莎仁等.Tb3+在燃烧法制备的CaLaAl3O7粉体中的发光性能[J].无机化学学报.2008.8.4
[50]刘金霞等.ZrO2:Tb3+纳米晶的制备与发光研究.人工晶体学报.2008.37.2
[51]Yang Chun, Zhang Junying. Red-Emitting Ga2O3.Eu3+ Powder Derived by Sol-GelProcessing. Journal of Rare Earths. June 2007, Vol25:90
[52]Guifang Li. Luminescence properties of YAl3(BO3)4 phosphors doped with Eu3+ ions. Journal of Rare Earths.2008 December. Vol26:792-4p.
[53]D.L. Dexter, Physical Review 108 (1956) 630.
[54]T. Forster, Ann. Physik 2 (1948) 55.
[55]Chung-Hsin Lu a, Wei-Tse Hsu a etc. J. Alloys Comps 2008; 456:57-63.
[2]李颖,赵永亮.稀土材料在高科技领域中的应用[J].内蒙古石油化工,2005,31(5)：9-11.
[3]卢利平.稀土发光材料[M].北京：国防工业出版社,2005,10-15.
[4]郑子樵,李红英.稀土功能材料[M].北京：化学工业出版社,2003.
[5]刘小珍.稀土精细化学品化学[M].北京：化学工业出版社,2009,7.
[6]徐光宪.稀土[M].北京：冶金工业出版社.1995,133.
[7]李建宇.稀土发光材料及其应用[M].北京：化学工业出版社,2003..
[8]莎仁,王喜贵.纳米晶LaAlO3掺Eu3+的复合沉淀制备及其光学性质的研究[J].影像科学与光化学.2009：27(6),435-440.
[9]F.Auzel,Compat,Rend.Acad.Connection between ture effective mass and optical absorption in insulator,Sci.Paris.1959,2:84-88.
[10]Auzel.F. Pecile D.Morin D,J Electrochem soc,1975,122(1),101.
[11]陈小波,宋增福.Er,Yb氟氧化物玻璃陶瓷的上转换发光特征饱和现象综合分析[J].光谱学与光谱分析.2005：25(2),161-165.
[12]沈毅,王少艳.上转换发光材料研究进展与应用[J].河北理工大学学报.2009：31(1),76-77.
[13]朱立刚,肖卓豪,卢安贤.上转换发光氧氟微晶研究进展.材料导报[J].2009：23(3),41
[14]乌兰图亚.稀土离子上转换发光研究进展[J].内蒙古石油化工.2007(12),19.
[15]何捍卫等.红外-可见光的上转换材料研究进展.中国稀土学报.2003：21(2),21.
[16]聂秋华.蓝绿光上转换荧光输出的稀土掺杂玻璃研究进展,硅酸盐通报2006.10；25(5).
[17]Yang Kui Sheng,Li Yan,Yu Chao Yi.upconversion luminescence of Ho3+,Tm3+,Yb3+co-doped Nanocrystal NaYF4 synthesized by Hydrothermal method[J] Journal of rare earths.2006(24):757-760.
[18]Yang Wei,Feng Qi Lu,Xinrong Zhang.Poly-mediated synthesis and luminescence of lanthanide-doped NaYF4 Nanocrystal upconversion phosphors[J] Journal of Alloy and compounds 455(2008),376-384.
[19]陈宝玖,王海宁,秦伟平等.高效的红外到可见上转换氟氧化物玻璃材料[J].光谱学与光谱分析.2003,20(3)：257.
[20]Kaczkan M, Frukcuz Z,Malinowskim. Infrared to visible wavelength upconversion in Sm3+-actived YAG crystal[J]. Journal of Alloy and compounds.2001,323-324:736.
[21]Fan WH,Hon X,Zhao W,etal.Effect of the growth conditions on infrared upconversion efficiency of CaS:Eu,Sm thin films[J].APPL,Phys A.2001,73:115.
[22]R.T.Wegh.Hdnker,KD.oskam,A.Meijerink.J.Alloys Comps 2000;97-89,1017.
[23]H.Y.Tzeng,B.M.cheng.T.M.chen,J.Lumin,122,(2007)917.
[24]李岩.稀土离子掺杂的NaYF4上转换纳米晶的制备与表征[D].2006.1
[25]张吉林,洪广言.稀土纳米发光材料研究进展[J].发光学报.2005：26(3)286-287.
[26]G.M.Qiu, Y.B. Sun, S.Q. Zhang, M. Zhang, C.H. Yan, S.J. Dai. Preparation and structure characterization of rare earth doped Alumina-siloxane gel and its modification on Er effect. Journal Of Rare Earths,2004;2,15.
[27]Xiao zhi guo.Long after glow silicate luminescent material and its manufacturing method[P].usp6093346.
[28]徐叙熔,苏勉曾.发光学与发光材料[M].北京：化学工业出版社,2004.
[29]M.J.weber.Journal Of Luminescence[J].100(2002)35.
[30]应跟裕,胡文波,邱勇.平板显示技术[M].北京：人民邮电出版社,2002.
[31]刘行仁.白光LED现状和问题.光源与照明.2003,3：4-8.
[32]王晓明,郭伟玲,高国等.LED-新一代照明光源[J].现代显示.2005(53)：15-19.
[33]J.P.countures.The Al2O3-Nd2O3 phase Diagram[J]. Journal of the American ceramic society.1985(68):105-107.
[34]罗岚,徐政,刘庆峰等.GdA103:Eu3+荧光粉燃烧合成及其光学性能.同济大学学报.2004,32(11)：1476-1479.
[35]Smets BMJ,BerlijsdonkJ G,The luminescence properties of Eu3+ and Mn2+ doped barium hexoaluminates,Material Reserch Bullitin,1986,21:1305-1310.
[36]Liu J R,Song L. Highly power Nd: Y3AL5O12 ceramic laser. Jpn. J. Appl. Phys.2000; 39: 1048-50p.
[37]张慰萍.稀土掺杂的纳米发光材料的制备和发光[J].发光学报2000;4(21)：314-9p.
[38]Jun Zhou, Yuhua Wang, Bitao Liu. Effect of H3BO3 on structure and photoluminescence of BaAl12O19:Mn2+ phosphor under VUV excitation.2009 Sepl8th;484:439-43p.
[39]董岩,张超,蒋建清,梁步清,刘凯,于金.掺杂元素对BaAI12019:Mn2+荧光粉发光性能的影响.东南大学学报(自然科学版)2005;35(6)：911-4p.
[40]李晓云,陆长天,梁爽.铝酸锶系长余辉发光粉的制备及其光学性能.南京化工大学学报,2001;23(2),32—35.
[41]袁鹏,李保平,王介强.微波均相沉淀法合成纳米粉体的研究进展.中国粉体技术2008.14.2.
[42]L. E. Shea. Synthesis of red-emitting, small particle size luminescent oxides using an optimize combustion process [J]. Journal of the American Ceramic Society 1996,79(32):57-61.
[43]S. Ekambaram, M. Maaza. Combustion synthesis and luminescent properties of Eu3+ activated cheap red phosphors [J]. J. Alloys Comps 2005; 395(1-2):132-4p.
[44]张世英,李德意,魏坤.溶胶凝胶法制备BaMgAl10O17:EU荧光粉的研究.中国陶瓷工业 2003;10(2):36—38p.
[45]Raviehandran D, Roy R, White W B. Synlhesis and Characterization of Sol-Gel Derived Hexa-Aluminate Phosphors[J]. Journal of Material Research 1997,12(3):819.
[46]R P. Rao. Tm3+ activated lanthanum phosphate: a blue PDP phosphor [J]. Journal of Luminescence 2005,113(3-4):271-8p.
[47]赵春燕,朱连杰,冯守华.BaBeF4:Sm3+的温和水热合成与光谱性质研究[J].高等学校化学学报,1998,19(7)：1023-25.
[48]陈江.Tb3+自敏化效应与Gd3+-Tb3+能量转移对硅酸盐玻璃发光性能的影响[J].玻璃与搪瓷.2009;37.3.
[49]莎仁等.Tb3+在燃烧法制备的CaLaAl3O7粉体中的发光性能[J].无机化学学报.2008.8.4
[50]刘金霞等.ZrO2:Tb3+纳米晶的制备与发光研究.人工晶体学报.2008.37.2
[51]Yang Chun, Zhang Junying. Red-Emitting Ga2O3.Eu3+ Powder Derived by Sol-GelProcessing. Journal of Rare Earths. June 2007, Vol25:90
[52]Guifang Li. Luminescence properties of YAl3(BO3)4 phosphors doped with Eu3+ ions. Journal of Rare Earths.2008 December. Vol26:792-4p.
[53]D.L. Dexter, Physical Review 108 (1956) 630.
[54]T. Forster, Ann. Physik 2 (1948) 55.
[55]Chung-Hsin Lu a, Wei-Tse Hsu a etc. J. Alloys Comps 2008; 456:57-63.