制备工艺对光激励发光材料BaFCl：Eu～（2+）发光性能的影响
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摘要
光激励发光材料作为一种新型的材料广泛应用在红外探测、成像、光存储、光学信息处理、辐射计量测定等方面。本论文首先对光激励发光材料的发展以及其结构特点做了简单介绍。对光激励发光材料的发光机理进行了总结与概括。着重描述了典型的光激励发光材料BaFCl:Eu2+在医疗影像版中的应用。
制备工艺是获得良好发光材料的关键。本文以BaCl2·2H2O,BaF2,Eu2O3为原料,以NH4Cl作为助熔剂,采用高温固相扩散的方法制备了BaFCl:Eu.并用X射线衍射的方法对产物进行了分析,证明了所得物质即为所需的产物。并通过改变助熔剂NH4Cl的配比、激活剂Eu离子的参杂比例、合成温度、烧结气氛、二次烧结、烧结状态和盛装容器等七个方面的实验条件,做了一系列实验,通过比较样品的发光性能发现它们的发光特性随条件的不同而有一定差异,从而得出了如下结论:在5%-7.5%的助熔剂NH4Cl配比下,激活剂Eu离子的参杂比例为0.004-0.006,烧结温度为750～900℃时,样品的发光强度最好。通过不同反应气氛的比较得知Eu3+的存在对Eu2+的发光起促进作用,二次烧结对增强样品的发光强度有利,用压片法制备的样品的发光性能优于直接粉末制备的方法,用石英材料盛装原料是较好的选择,并且对得出的结论进行了理论分析。
Photostimulated luminesence materials were applied extensively to the fields of IR detection, digital imaging, photomemory, information storage, dosimetry, and so on as a new kind of luminesence material. This paper presents an introduction of the development and the structure characteristic of the phostostimulated materials,besides sum up their luminescence mechanism. The typical photostiumlated luminesence material BaFCl:Eu has been used in the medical image plate.
Preparation process is the key of getting good luminesence material. In this paper, BaFCl:Eu was prepared with high temperature solid diffusion process. BaCl2·2H2O,BaF2 and Eu2O3 was the raw material,NH4Cl was the melt-suppporting agent. A series of experiments were carried out.They were the proportion of NH4Cl, the proportion of Eu ion, synthetize temperature, calcinations atmosphere, dual-calcination process,calcinations state and container.Through comparing their luminesence efficiency,there are some difference luminesence efficiency if it was prepared by different experiment conditions.So some conclusions were drawn in this paper: when the proportion of fusing agent NH4Cl is 5~7%, the mole proportion of Eu ion is 0.004~0.006,calcinations temperature is 750~900℃,luminesence material BaFCl:Eu have the best luminesence efficiency.Results also showed that Eu3+ can promote the luminescence of Eu2+,and the dual-calcination process can also improve its efficiency.The sample’s luminescence efficiency with pressing sheet is better than powder.Quartaz material is better for the luminescence efficiency.A theoretical interpretation is briefly elucidated also.
制备工艺是获得良好发光材料的关键。本文以BaCl2·2H2O,BaF2,Eu2O3为原料,以NH4Cl作为助熔剂,采用高温固相扩散的方法制备了BaFCl:Eu.并用X射线衍射的方法对产物进行了分析,证明了所得物质即为所需的产物。并通过改变助熔剂NH4Cl的配比、激活剂Eu离子的参杂比例、合成温度、烧结气氛、二次烧结、烧结状态和盛装容器等七个方面的实验条件,做了一系列实验,通过比较样品的发光性能发现它们的发光特性随条件的不同而有一定差异,从而得出了如下结论:在5%-7.5%的助熔剂NH4Cl配比下,激活剂Eu离子的参杂比例为0.004-0.006,烧结温度为750～900℃时,样品的发光强度最好。通过不同反应气氛的比较得知Eu3+的存在对Eu2+的发光起促进作用,二次烧结对增强样品的发光强度有利,用压片法制备的样品的发光性能优于直接粉末制备的方法,用石英材料盛装原料是较好的选择,并且对得出的结论进行了理论分析。
Photostimulated luminesence materials were applied extensively to the fields of IR detection, digital imaging, photomemory, information storage, dosimetry, and so on as a new kind of luminesence material. This paper presents an introduction of the development and the structure characteristic of the phostostimulated materials,besides sum up their luminescence mechanism. The typical photostiumlated luminesence material BaFCl:Eu has been used in the medical image plate.
Preparation process is the key of getting good luminesence material. In this paper, BaFCl:Eu was prepared with high temperature solid diffusion process. BaCl2·2H2O,BaF2 and Eu2O3 was the raw material,NH4Cl was the melt-suppporting agent. A series of experiments were carried out.They were the proportion of NH4Cl, the proportion of Eu ion, synthetize temperature, calcinations atmosphere, dual-calcination process,calcinations state and container.Through comparing their luminesence efficiency,there are some difference luminesence efficiency if it was prepared by different experiment conditions.So some conclusions were drawn in this paper: when the proportion of fusing agent NH4Cl is 5~7%, the mole proportion of Eu ion is 0.004~0.006,calcinations temperature is 750~900℃,luminesence material BaFCl:Eu have the best luminesence efficiency.Results also showed that Eu3+ can promote the luminescence of Eu2+,and the dual-calcination process can also improve its efficiency.The sample’s luminescence efficiency with pressing sheet is better than powder.Quartaz material is better for the luminescence efficiency.A theoretical interpretation is briefly elucidated also.
引文
[1] Bates, C. W.; Eidson, J.; John, C.; Image intensifier plate and compositions, US, 3855035, 1974-12-17
[2] Iwabuchi, Y., Method for processing electric signals of radiographic image recorded in stimulable phosphor sheet, Eur. Pat. Appl., JP, 1031854, 2000-08-30
[3].Horikawa, K., Radiation image read-out method, US, 4571493, 1986-02-18
[4].徐征 王永生 赵辉等,光激励发光材料 BaFCl:Eu 的制备及电子能谱,北方交通大学学报,1997,21(4),445-448
[5].范文慧 刘英 王永昌等,制备工艺对电子俘获材料性能的影响,光子学报,1998,9,855-858
[6].陈伟 马如璋 苏勉曾,BaFCl:Eu2+,Eu3+的光激励发光过程,无机材料学报,9(1),22-25
[7].王永生 熊光楠 徐叙瑢等,Eu2+:BaFCl 光激励发光过程中紫外线的激发与漂白效应,光学学报,1995,15(8),1123-1126
[8].王永生 张光寅 张雪强等,紫外线辐照能量对 BaFCl:Eu2+光激励发光的影响,红外与毫米波学报,1995,14(4),295-298
[9].王永生 熊光楠 徐叙瑢,紫外辐照下的 BaFCl:Eu2+光激励发光的研究,自然科学进展,1993,3(3),271-274
[10]. 陈伟 宋家庆 苏勉曾, X 射线影像存储与再现用发光材料MFX:Eu2+的研究现状及应用前景,功能材料,1994,25(3),197-205
[11].史锦珊 郑绳楦,光电子学及其应用,机械工业出版社,北京,1991,123-126
[12].SteveleA. Pingault P. Philips Rep. 1975,30,227
[13].J.Lindmayer,A new erasable optical memory. Solid State Tech.,1988,31(8),135-138
[14] H Nanto,F Endo. Eu-doped KCl phosphor crystals as a storage material for two-dim ensional ultravioler-tay or x-ray imaging sensor J Appl phys 1994,75(11):7493
[15].干福熹 邓佩珍, 激光材料,上海科学技术出版社,上海,1996,197-205
[16].Kalpana,G. Palanivel,B. Venkatasubramaniam,K etc,A Structural Study on MFCl(M=Ca,Sr,Ba) and BaFX(X=Br,I),Bulletin of materials science, 1997,20(4),461-465
[17].王永生 熊光楠,F/Cl 比与 BaFCl:Eu 中 F 色心的浓度和光激励截面的关系,光学学报,1995,15(8),1124-1126
[18].Toshio,K. Shuichi,K.Yukio,H.,etc,Origin of F-aggregate Centers in BaFX(X=Cl,Br) Single Crystals,Jpn.J.Appl.Phys.,1998,37,812-815
[19].Spaeth J.M. Hangleiter Th. Koschnick F.K.,etc.,X-ray storage phosphors,Radiat Effects Defects Solids,1995,135,499-508
[20].范文慧 叶孔敦 光昕等, 电子俘获材料在光存储技术中的应用, 半导体光电 ,2001,22(3),161-165
[21].阮昊 陈述春 戴凤妹等,电子俘获材料在光记录中的应用,感光科学与光化学,1997,15(1),54-58
[22].赵辉 王永生 徐征等,电子俘获材料读写关系的理论研究,北方交通大学学报,1998,22(2),33-36
[23].李海玲 王永生 孙力等,电子俘获材料在光信息处理中的应用,北方交通大学学报,2001,25(6),38-41.
[24].郝润蓉 方锡义,无机化学丛书(第三册),科学出版社,1998,473-474
[25].Takahashi K,Kohda K,Shionya S. Extented Abstracts,Fall Meeting of Electrochem.soc.,1986,692
[26].Takahashi K,Miyahara J,Shibahara Y. Photostimulated luminescence(PSL) and color centers in BaFX:Eu2+(X=Cl,Br,I) phosphors,Journal of the Electrochemical Society: Solid state science and Technology,1985,132(6),1492-1494.
[27].Von Seggern H, Voigyt T. Physical model of photostimulated luminescence of X-ray irradiated BaFCl:Eu2+,J.Appl.Phys.1988,64(3),1405-1412.
[28].王永生 赵辉,BaFCl:Eu2+光激励发光衰减的研究,光学学报,1998,18(2),208
[29].Yongsheng Wang,Hui Zhao, Temperature effect of two kinds of color centers in BaFCl:Eu2+ phosphors in photostimulated readout process Physica B, 1999,269(3-4),310
[30].孙力 王永生 董金凤等,电子俘获光存储材料的研究进展,激光与红外,2001,31(5),262-265
[31].赵辉 王永生 徐征等,光激励发光的并行模型,物理学报 1998(2)333-339
[32] Hall, C. J.; Lewis, R. A.; Parker, B.; etc., The secret life of image plate phosphors. Rev.Sci.Instrum, 1992, 63(1,Pt. 2A), 697-699
[33] Suzuki, T.; Mori, C.; Yanagida, K.; etc., Characteristics and correction of the fading of imaging plate, J.Nucl. Sci. Technol., 1997, 34(5), 461-465
[34].李建宇,稀土发光材料及其应用,化学工业出版社,北京,2003,9,338
[35].王林同 王世华 赵新华,含 Eu2+固体的荧光光谱研究及其应用,化学通报,1997,5,30-37
[36] 范文慧 王永昌 侯洵等,电子俘获材料和皮秒红外脉冲激励发光,中国激光,1999,26(1),22-25
[37].陈伟 宋家庆 苏勉曾,发光材料 BaFCl:Eu 的穆斯堡尔谱研究,物理化学学报,1994,8,692-696
[38].王永生 熊光楠 徐叙瑢等,X 射线影像存储材料 BaFxCl2-x:Eu2+的制备及其热释发光和光激励发光,功能材料,1995,26(1),44-47
[2] Iwabuchi, Y., Method for processing electric signals of radiographic image recorded in stimulable phosphor sheet, Eur. Pat. Appl., JP, 1031854, 2000-08-30
[3].Horikawa, K., Radiation image read-out method, US, 4571493, 1986-02-18
[4].徐征 王永生 赵辉等,光激励发光材料 BaFCl:Eu 的制备及电子能谱,北方交通大学学报,1997,21(4),445-448
[5].范文慧 刘英 王永昌等,制备工艺对电子俘获材料性能的影响,光子学报,1998,9,855-858
[6].陈伟 马如璋 苏勉曾,BaFCl:Eu2+,Eu3+的光激励发光过程,无机材料学报,9(1),22-25
[7].王永生 熊光楠 徐叙瑢等,Eu2+:BaFCl 光激励发光过程中紫外线的激发与漂白效应,光学学报,1995,15(8),1123-1126
[8].王永生 张光寅 张雪强等,紫外线辐照能量对 BaFCl:Eu2+光激励发光的影响,红外与毫米波学报,1995,14(4),295-298
[9].王永生 熊光楠 徐叙瑢,紫外辐照下的 BaFCl:Eu2+光激励发光的研究,自然科学进展,1993,3(3),271-274
[10]. 陈伟 宋家庆 苏勉曾, X 射线影像存储与再现用发光材料MFX:Eu2+的研究现状及应用前景,功能材料,1994,25(3),197-205
[11].史锦珊 郑绳楦,光电子学及其应用,机械工业出版社,北京,1991,123-126
[12].SteveleA. Pingault P. Philips Rep. 1975,30,227
[13].J.Lindmayer,A new erasable optical memory. Solid State Tech.,1988,31(8),135-138
[14] H Nanto,F Endo. Eu-doped KCl phosphor crystals as a storage material for two-dim ensional ultravioler-tay or x-ray imaging sensor J Appl phys 1994,75(11):7493
[15].干福熹 邓佩珍, 激光材料,上海科学技术出版社,上海,1996,197-205
[16].Kalpana,G. Palanivel,B. Venkatasubramaniam,K etc,A Structural Study on MFCl(M=Ca,Sr,Ba) and BaFX(X=Br,I),Bulletin of materials science, 1997,20(4),461-465
[17].王永生 熊光楠,F/Cl 比与 BaFCl:Eu 中 F 色心的浓度和光激励截面的关系,光学学报,1995,15(8),1124-1126
[18].Toshio,K. Shuichi,K.Yukio,H.,etc,Origin of F-aggregate Centers in BaFX(X=Cl,Br) Single Crystals,Jpn.J.Appl.Phys.,1998,37,812-815
[19].Spaeth J.M. Hangleiter Th. Koschnick F.K.,etc.,X-ray storage phosphors,Radiat Effects Defects Solids,1995,135,499-508
[20].范文慧 叶孔敦 光昕等, 电子俘获材料在光存储技术中的应用, 半导体光电 ,2001,22(3),161-165
[21].阮昊 陈述春 戴凤妹等,电子俘获材料在光记录中的应用,感光科学与光化学,1997,15(1),54-58
[22].赵辉 王永生 徐征等,电子俘获材料读写关系的理论研究,北方交通大学学报,1998,22(2),33-36
[23].李海玲 王永生 孙力等,电子俘获材料在光信息处理中的应用,北方交通大学学报,2001,25(6),38-41.
[24].郝润蓉 方锡义,无机化学丛书(第三册),科学出版社,1998,473-474
[25].Takahashi K,Kohda K,Shionya S. Extented Abstracts,Fall Meeting of Electrochem.soc.,1986,692
[26].Takahashi K,Miyahara J,Shibahara Y. Photostimulated luminescence(PSL) and color centers in BaFX:Eu2+(X=Cl,Br,I) phosphors,Journal of the Electrochemical Society: Solid state science and Technology,1985,132(6),1492-1494.
[27].Von Seggern H, Voigyt T. Physical model of photostimulated luminescence of X-ray irradiated BaFCl:Eu2+,J.Appl.Phys.1988,64(3),1405-1412.
[28].王永生 赵辉,BaFCl:Eu2+光激励发光衰减的研究,光学学报,1998,18(2),208
[29].Yongsheng Wang,Hui Zhao, Temperature effect of two kinds of color centers in BaFCl:Eu2+ phosphors in photostimulated readout process Physica B, 1999,269(3-4),310
[30].孙力 王永生 董金凤等,电子俘获光存储材料的研究进展,激光与红外,2001,31(5),262-265
[31].赵辉 王永生 徐征等,光激励发光的并行模型,物理学报 1998(2)333-339
[32] Hall, C. J.; Lewis, R. A.; Parker, B.; etc., The secret life of image plate phosphors. Rev.Sci.Instrum, 1992, 63(1,Pt. 2A), 697-699
[33] Suzuki, T.; Mori, C.; Yanagida, K.; etc., Characteristics and correction of the fading of imaging plate, J.Nucl. Sci. Technol., 1997, 34(5), 461-465
[34].李建宇,稀土发光材料及其应用,化学工业出版社,北京,2003,9,338
[35].王林同 王世华 赵新华,含 Eu2+固体的荧光光谱研究及其应用,化学通报,1997,5,30-37
[36] 范文慧 王永昌 侯洵等,电子俘获材料和皮秒红外脉冲激励发光,中国激光,1999,26(1),22-25
[37].陈伟 宋家庆 苏勉曾,发光材料 BaFCl:Eu 的穆斯堡尔谱研究,物理化学学报,1994,8,692-696
[38].王永生 熊光楠 徐叙瑢等,X 射线影像存储材料 BaFxCl2-x:Eu2+的制备及其热释发光和光激励发光,功能材料,1995,26(1),44-47