新型Gd_2SiO_5∶RE荧光粉的制备和发光性能
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摘要
以Gd_2O_3、SiO、稀土氧化物为原料采用高温固相法制备了Gd_(2(1-x))SiO_5∶2xRE荧光粉体。X射线衍射分析结果表明Gd/Si配比为1.9,BaF_2助熔剂用量为5‰,煅烧条件为1500℃保温3h得到结晶良好的Gd_2SiO_5及Gd_2SiO_5∶RE粉体。光谱分析表明,Gd_2SiO_5∶Eu荧光粉末激发波段为250～470nm,而Gd_2SiO_5∶Tb为250～320nm;前者发射主峰为620nm(与Eu~(3+)的~5D_0→~7F_2对应),后者为548nm(与Tb~(3+)的~5D_4→~7F_5对应);Eu~(3+)和Tb~(3+)的最佳掺杂量为7%。f_a(E)和发射带f_e(E)交叠越大,则电偶极-电偶极作用机制的跃迁几率越高,Gd~(3+)-Tb~(3+)能带交叠程度大于Gd~(3+)-Eu~(3+),Tb~(3+)的量子效率要高于Eu~(3+)。
Gd_2SiO_5∶ RE phosphors were prepared by high temperature solid-state method with Gd_2O_3 and Si O as the raw material. The effects of calcining temperature,Gd/Si atomic ratio and fluxing agent on the Gd_2SiO_5 crystallized power fabrication were studied systematically,by means of X-ray diffraction( XRD). The optimum calcining condition is holding at 1 500 ℃ for 3 h with Gd/Si atom ratio of 1. 9,and Ba F_2 of 5‰ used as flux. Photoluminescent spectra show that the excitation rang is 250-470 nm for Gd_2SiO_5∶ Eu,while 250-320 nm for Gd_2SiO_5∶ Tb. The strongest peak in the emission spectra is 620 nm( related to Eu~(3+):~5D_0→~7F_2) for the former phosphor. For the later phosphor,the strongest peak locates at 548 nm( related to Tb~(3+):~5D_4→~7F_5). The best doping amount is 7% for Eu~(3+) and 5% Tb~(3+). The collaboration of fa( E) and fe( E) for Gd~(3+)-Tb~(3+) is better than that of Gd~(3+)-Eu~(3+),so the Gd_2SiO_5∶xTb will have higher quantum yields than Gd_2SiO_5∶xTb.
Gd_2SiO_5∶ RE phosphors were prepared by high temperature solid-state method with Gd_2O_3 and Si O as the raw material. The effects of calcining temperature,Gd/Si atomic ratio and fluxing agent on the Gd_2SiO_5 crystallized power fabrication were studied systematically,by means of X-ray diffraction( XRD). The optimum calcining condition is holding at 1 500 ℃ for 3 h with Gd/Si atom ratio of 1. 9,and Ba F_2 of 5‰ used as flux. Photoluminescent spectra show that the excitation rang is 250-470 nm for Gd_2SiO_5∶ Eu,while 250-320 nm for Gd_2SiO_5∶ Tb. The strongest peak in the emission spectra is 620 nm( related to Eu~(3+):~5D_0→~7F_2) for the former phosphor. For the later phosphor,the strongest peak locates at 548 nm( related to Tb~(3+):~5D_4→~7F_5). The best doping amount is 7% for Eu~(3+) and 5% Tb~(3+). The collaboration of fa( E) and fe( E) for Gd~(3+)-Tb~(3+) is better than that of Gd~(3+)-Eu~(3+),so the Gd_2SiO_5∶xTb will have higher quantum yields than Gd_2SiO_5∶xTb.
引文
[1]赵景泰.闪烁晶体材料的研究进展[J].中国材料进展,2010,29(10):40-48.ZHAO J T. Research development of inorganic scintillating crystals[J]. Mater. China,2010,29(10):40-48.(in Chinese)
[2]张涵.浅析掺杂硅酸钆晶体的研究现状[J].科技信息,2014(8):74-76.ZHANG H. The present research situation of doped gadolinium silicate crystals[J]. Sci. Technol. Inf.,2014(8):74-76.(in Chinese)
[3]张涵.硅酸钆晶体的点缺陷研究[D].上海:上海理工大学,2013.ZHANG H. Study of The Point Defect in The Gd2Si O5Crystal[D]. Shanghai:Shanghai University of Technology,2013.(in Chinese)
[4]TAKAGI K,FUKAZAWA T. Cerium-activated Gd2Si O5single crystal scintillator[J]. Appl. Phys. Lett.,1983,42(1):43-45.
[5]YAN C F,ZHAO G J,SU L B,et al.. Growth and spectroscopic characteristics of Yb∶GSO single crystal[J]. J. Phys.:Condens. Mat.,2006,18(4):1325-1333.
[6]霍涌前,汪英杰,任筱筱,等. Eu3+、Gd3+共掺杂Sr2Si O4荧光粉的液相沉淀合成及能量转移发光性能[J].合成材料老化与应用,2016,45(1):68-72.HUO Y Q,WANG Y J,REN X X,et al.. Fabrication of Eu3+and Gd3+Codoped Sr2Si O4via precipitation method and their photoluminescence properties through energy transfer[J]. Synth. Mater. Aging Appl.,2016,45(1):68-72.(in Chinese)
[7]廉锐,尹民,张慰萍,等.纳米YPO4∶Pr3+的化学制备、结构分析和光谱特性[J].发光学报,1999,20(2):102-105.LIAN R,YIN M,ZHANG W P,et al.. Chemical preparation,structure analysis and spectrum characteristics of YPO4∶Pr3+nanocrystal[J]. Chin. J. Lumin.,1999,20(2):102-105.(in Chinese)
[8]WANG H,HOU Q,HUANG J H,et al.. Polarized spectroscopic properties and continuous-wave laser operation of Yb∶Gd2Si O5crystal[J]. J. Alloys Compd.,2016,683:554-558.
[9]罗岚,陈栋,黄权. Gd Al O3∶Tb,RE中Tb,RE的能量传递研究[J].影像科学与光化学,2008,26(3):233-237.LUO L,CHEN D,HUANG Q. Energy transfer between Tb and RE in Gd Al O3∶Tb,RE[J]. Imaging Sci. Photochem.,2008,26(3):233-237.(in Chinese)
[10]孙文周,陈宇红,黄振坤,等. Si C基陶瓷高温相平衡——Si C-Si3N4-Gd2O3系统[J].硅酸盐学报,2011,39(10):1536-1540.SUN W Z,CHEN Y H,HUANG Z K,et al.. High temperature phase equlibrium of silicon carbide based ceramics—phase relations of Si C-Si3N4-Gd2O3system[J]. J. Chin. Ceram. Soc.,2011,39(10):1536-1540.(in Chinese)
[11]龚显年,黄荣榕,谢永纯,等.原料配比对合成一氧化锰/碳微球结构和性能的影响[J].无机盐工业,2018,50(3):20-25.GONG X N,HUANG R R,XIE Y C,et al.. Effects of the mix ratio of raw materials on structure and performance of porous MnO/C microspheres[J]. Inorg. Chem. Ind.,2018,50(3):20-25.(in Chinese)
[12]孙海鹰,张希艳,王烨蛟. Gd2Si O5∶Eu3+红色荧光粉的制备与发光性能的研究[J].长春理工大学学报(自然科学版),2013,36(1-2):87-89.SUN H Y,ZHANG X Y,WANG Y J. Study on the optical properties and preparation of Gd2Si O5∶Eu3+red phosphor[J].J. Changchun Univ. Sci. Technol.(Nat. Sci. Ed.),2013,36(1-2):87-89.(in Chinese)
[13]董婷婷.白光LED用稀土荧光粉体的制备及发光性能研究[D].长春:吉林大学,2014.DONG T T. Synthesis and Luminescence Properties of Phosphor Doped with Rare Earth Ion for White LED[D]. Changchun:Jilin University,2014.(in Chinese)
[14]李世普.特种陶瓷工艺学[M].武汉:武汉工业大学出版社,1990:63-68.LI S P. Special Cerramic Technology[M]. Wuhan:Wuhan Industrial University Press,1990:63-68.(in Chinese)
[15]TAMRAKAR R K,UPADHYAY K. Photoluminescence behaviour of Gd2Si O5phosphor[J]. Optik,2016,127(13):5204-5206.
[16]PARGANIHA Y,KAUR J,DUBEY V,et al.. Violet blue emission and thermoluminescence glow curve analysis of Gd2Si O5∶Ce3+phosphor[J]. Optik,2016,127(15):6243-6252.
[17]李霞.稀土离子RE3+(RE=Eu,Tb)与Na2WO4共掺杂的Si O2发光材料的制备及其发光性质的研究[D].呼和浩特:内蒙古师范大学,2007.LI X. Preparation and Luminescence Properties of RE3+(RE=Eu,Tb)and Na2WO4Co-doped Si O2Materials[D]. Hohhot:Inner Mongolia Normal University,2007.(in Chinese)
[18]杨志平,马淑媛,于红伟,等.绿色荧光粉Zn2Ca(PO4)2∶Tb3+的制备及发光性能研究[J].功能材料,2010,41(7):1228-1231.YANGZ P,MA S Y,YU H W,et al.. Preparation and luminescent properties of Zn2Ca(PO4)2∶Tb3+green phosphor[J].J. Funct. Mater.,2010,41(7):1228-1231.(in Chinese)
[19]YATSIMIRSKII K B,DAVIDENKO N K. Absorption spectra and structure of lanthanide coordination compounds in solution[J]. Coordin. Chem. Rev.,1979,27(3):223-273.
[20]AUZEL F,PELLF. Concentration and excitation effects in multiphonon non-radiative transitions of rare-earth ions[J].J. Lumin.,1996,69(5-6):249-255.
[21]DEXTER D L. A theory of sensitized luminescence in solids[J]. J. Chem. Phys.,1953,21(5):836-850.
[2]张涵.浅析掺杂硅酸钆晶体的研究现状[J].科技信息,2014(8):74-76.ZHANG H. The present research situation of doped gadolinium silicate crystals[J]. Sci. Technol. Inf.,2014(8):74-76.(in Chinese)
[3]张涵.硅酸钆晶体的点缺陷研究[D].上海:上海理工大学,2013.ZHANG H. Study of The Point Defect in The Gd2Si O5Crystal[D]. Shanghai:Shanghai University of Technology,2013.(in Chinese)
[4]TAKAGI K,FUKAZAWA T. Cerium-activated Gd2Si O5single crystal scintillator[J]. Appl. Phys. Lett.,1983,42(1):43-45.
[5]YAN C F,ZHAO G J,SU L B,et al.. Growth and spectroscopic characteristics of Yb∶GSO single crystal[J]. J. Phys.:Condens. Mat.,2006,18(4):1325-1333.
[6]霍涌前,汪英杰,任筱筱,等. Eu3+、Gd3+共掺杂Sr2Si O4荧光粉的液相沉淀合成及能量转移发光性能[J].合成材料老化与应用,2016,45(1):68-72.HUO Y Q,WANG Y J,REN X X,et al.. Fabrication of Eu3+and Gd3+Codoped Sr2Si O4via precipitation method and their photoluminescence properties through energy transfer[J]. Synth. Mater. Aging Appl.,2016,45(1):68-72.(in Chinese)
[7]廉锐,尹民,张慰萍,等.纳米YPO4∶Pr3+的化学制备、结构分析和光谱特性[J].发光学报,1999,20(2):102-105.LIAN R,YIN M,ZHANG W P,et al.. Chemical preparation,structure analysis and spectrum characteristics of YPO4∶Pr3+nanocrystal[J]. Chin. J. Lumin.,1999,20(2):102-105.(in Chinese)
[8]WANG H,HOU Q,HUANG J H,et al.. Polarized spectroscopic properties and continuous-wave laser operation of Yb∶Gd2Si O5crystal[J]. J. Alloys Compd.,2016,683:554-558.
[9]罗岚,陈栋,黄权. Gd Al O3∶Tb,RE中Tb,RE的能量传递研究[J].影像科学与光化学,2008,26(3):233-237.LUO L,CHEN D,HUANG Q. Energy transfer between Tb and RE in Gd Al O3∶Tb,RE[J]. Imaging Sci. Photochem.,2008,26(3):233-237.(in Chinese)
[10]孙文周,陈宇红,黄振坤,等. Si C基陶瓷高温相平衡——Si C-Si3N4-Gd2O3系统[J].硅酸盐学报,2011,39(10):1536-1540.SUN W Z,CHEN Y H,HUANG Z K,et al.. High temperature phase equlibrium of silicon carbide based ceramics—phase relations of Si C-Si3N4-Gd2O3system[J]. J. Chin. Ceram. Soc.,2011,39(10):1536-1540.(in Chinese)
[11]龚显年,黄荣榕,谢永纯,等.原料配比对合成一氧化锰/碳微球结构和性能的影响[J].无机盐工业,2018,50(3):20-25.GONG X N,HUANG R R,XIE Y C,et al.. Effects of the mix ratio of raw materials on structure and performance of porous MnO/C microspheres[J]. Inorg. Chem. Ind.,2018,50(3):20-25.(in Chinese)
[12]孙海鹰,张希艳,王烨蛟. Gd2Si O5∶Eu3+红色荧光粉的制备与发光性能的研究[J].长春理工大学学报(自然科学版),2013,36(1-2):87-89.SUN H Y,ZHANG X Y,WANG Y J. Study on the optical properties and preparation of Gd2Si O5∶Eu3+red phosphor[J].J. Changchun Univ. Sci. Technol.(Nat. Sci. Ed.),2013,36(1-2):87-89.(in Chinese)
[13]董婷婷.白光LED用稀土荧光粉体的制备及发光性能研究[D].长春:吉林大学,2014.DONG T T. Synthesis and Luminescence Properties of Phosphor Doped with Rare Earth Ion for White LED[D]. Changchun:Jilin University,2014.(in Chinese)
[14]李世普.特种陶瓷工艺学[M].武汉:武汉工业大学出版社,1990:63-68.LI S P. Special Cerramic Technology[M]. Wuhan:Wuhan Industrial University Press,1990:63-68.(in Chinese)
[15]TAMRAKAR R K,UPADHYAY K. Photoluminescence behaviour of Gd2Si O5phosphor[J]. Optik,2016,127(13):5204-5206.
[16]PARGANIHA Y,KAUR J,DUBEY V,et al.. Violet blue emission and thermoluminescence glow curve analysis of Gd2Si O5∶Ce3+phosphor[J]. Optik,2016,127(15):6243-6252.
[17]李霞.稀土离子RE3+(RE=Eu,Tb)与Na2WO4共掺杂的Si O2发光材料的制备及其发光性质的研究[D].呼和浩特:内蒙古师范大学,2007.LI X. Preparation and Luminescence Properties of RE3+(RE=Eu,Tb)and Na2WO4Co-doped Si O2Materials[D]. Hohhot:Inner Mongolia Normal University,2007.(in Chinese)
[18]杨志平,马淑媛,于红伟,等.绿色荧光粉Zn2Ca(PO4)2∶Tb3+的制备及发光性能研究[J].功能材料,2010,41(7):1228-1231.YANGZ P,MA S Y,YU H W,et al.. Preparation and luminescent properties of Zn2Ca(PO4)2∶Tb3+green phosphor[J].J. Funct. Mater.,2010,41(7):1228-1231.(in Chinese)
[19]YATSIMIRSKII K B,DAVIDENKO N K. Absorption spectra and structure of lanthanide coordination compounds in solution[J]. Coordin. Chem. Rev.,1979,27(3):223-273.
[20]AUZEL F,PELLF. Concentration and excitation effects in multiphonon non-radiative transitions of rare-earth ions[J].J. Lumin.,1996,69(5-6):249-255.
[21]DEXTER D L. A theory of sensitized luminescence in solids[J]. J. Chem. Phys.,1953,21(5):836-850.