磷灰石结构荧光粉Ba_(10)(PO_4)_6F_2∶Ce~(3+),Tb~(3+)的合成、发光和能量传递
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摘要
采用高温固相法合成了系列Ce~(3+)和Ce~(3+)/Tb~(3+)激活的具有磷灰石结构荧光粉Ba_(10)(PO_4)_6F_2。用X射线衍射(XRD)、扫描电镜(SEM)、激发和发射(PLE和PL)光谱对样品进行了表征分析。研究结果表明:所合成的荧光粉Ba_(10)(PO_4)_6F_2∶Ce~(3+),Tb~(3+)具有氟磷灰石结构,样品微观呈现不规则形貌。荧光粉Ba10-x(PO4)6F2∶x Ce~(3+)的相对发射强度随着x增加而增强,当x=0.09时,荧光强度达到最大。荧光粉Ba_(10)(PO_4)_6F_2∶Ce~(3+),Tb~(3+)的激发光谱为240～330 nm的宽带,发射光谱呈现出Ce~(3+)的5d→4f跃迁紫外光(335和358 nm)发射和Tb~(3+)的4f→4f跃迁绿光(542 nm)发射。光谱特性表明,发光过程中存在Ce~(3+)→Tb~(3+)能量传递,能量传递效率可以达到60%。计算Ce~(3+)和Tb~(3+)的临界距离为0.79 nm,能量传递机理是偶极-偶极交互作用。此外,详细论述了Ce~(3+)和Tb~(3+)之间的能量传递和发光的过程。通过调节Tb~(3+)的掺杂浓度,对荧光粉发光色坐标与Tb~(3+)的掺杂浓度之间的关系也进行了研究,随着Tb~(3+)的掺杂量从0增加0.52,荧光粉Ba_(10)(PO_4)_6F_2∶Ce~(3+),Tb~(3+)的发射光谱色坐标可以从(0.149 4,0.045 1)蓝色区变化到(0.280 1,0.585 3)绿色区。
A series of Ce~(3+)-and Ce~(3+)/Tb~(3+)-activated Ba_(10)(PO_4)_6F_2phosphors with apatite structure have been synthesized via high temperature solid-state reaction. X-ray diffraction(XRD), scanning electron microscopy(SEM), the photoluminenscence excitation(PLE) spectra and photoluminescence(PL) spectra were used to characterize samples. The results revealed that the fluorapatite structured Ba_(10)(PO_4)_6F_2∶Ce~(3+),Tb~(3+)phosphor particles with irregular morphology have been obtained. The relative intensities of PL spectra of Ba10-x(PO4)6F2:x Ce~(3+)phosphors increased with increasing x values, and reached the maximum at x=0.09. The as-prepared phosphors Ba_(10)(PO_4)_6F_2∶Ce~(3+),Tb~(3+)phosphors exhibited broad excitation band ranging from 240 to 330 nm. The emission spectra of Ba_(10)(PO_4)_6F_2∶Ce~(3+),Tb~(3+)phosphor showed the violet-emitting band centered at 335 and 358 nm and green light-emitting band centered at 542 nm, which originate from the 5d→4f transitions of Ce~(3+)and 4f→4f transitions of Tb~(3+), respectively.The spectral characteristics showed that the energy transfer occurs from Ce~(3+)to Tb~(3+)in Ba_(10)(PO_4)_6F_2∶Ce~(3+),Tb3 +phosphors, and the energy transfer efficiency between Ce3 +and Tb3 +could reach up to 60%. The critical distance of Ce~(3+)and Tb~(3+)was calculated to be 0.79 nm, and the mechanism of energy transfer from Ce~(3+)to Tb~(3+)is dipole-dipole interaction. In addition, the energy transfer behavior and luminescence process were discussed in detail. By adjusting the concentration of Tb3 +, the relationship between chromatic coordinate and the doping concentration of Tb~(3+)was studied. The Ba_(10)(PO_4)_6F_2∶Ce~(3+),Tb~(3+)phosphors emission color could adjust from blue to green, and the chromatic coordinate tuned from(0.149 4, 0.045 1) to(0.280 1, 0.585 3) with increasing the concentration of Tb~(3+)from 0 to 0.52.
A series of Ce~(3+)-and Ce~(3+)/Tb~(3+)-activated Ba_(10)(PO_4)_6F_2phosphors with apatite structure have been synthesized via high temperature solid-state reaction. X-ray diffraction(XRD), scanning electron microscopy(SEM), the photoluminenscence excitation(PLE) spectra and photoluminescence(PL) spectra were used to characterize samples. The results revealed that the fluorapatite structured Ba_(10)(PO_4)_6F_2∶Ce~(3+),Tb~(3+)phosphor particles with irregular morphology have been obtained. The relative intensities of PL spectra of Ba10-x(PO4)6F2:x Ce~(3+)phosphors increased with increasing x values, and reached the maximum at x=0.09. The as-prepared phosphors Ba_(10)(PO_4)_6F_2∶Ce~(3+),Tb~(3+)phosphors exhibited broad excitation band ranging from 240 to 330 nm. The emission spectra of Ba_(10)(PO_4)_6F_2∶Ce~(3+),Tb~(3+)phosphor showed the violet-emitting band centered at 335 and 358 nm and green light-emitting band centered at 542 nm, which originate from the 5d→4f transitions of Ce~(3+)and 4f→4f transitions of Tb~(3+), respectively.The spectral characteristics showed that the energy transfer occurs from Ce~(3+)to Tb~(3+)in Ba_(10)(PO_4)_6F_2∶Ce~(3+),Tb3 +phosphors, and the energy transfer efficiency between Ce3 +and Tb3 +could reach up to 60%. The critical distance of Ce~(3+)and Tb~(3+)was calculated to be 0.79 nm, and the mechanism of energy transfer from Ce~(3+)to Tb~(3+)is dipole-dipole interaction. In addition, the energy transfer behavior and luminescence process were discussed in detail. By adjusting the concentration of Tb3 +, the relationship between chromatic coordinate and the doping concentration of Tb~(3+)was studied. The Ba_(10)(PO_4)_6F_2∶Ce~(3+),Tb~(3+)phosphors emission color could adjust from blue to green, and the chromatic coordinate tuned from(0.149 4, 0.045 1) to(0.280 1, 0.585 3) with increasing the concentration of Tb~(3+)from 0 to 0.52.
引文
[1] Li G G, Lin C C, Wei Y, et al. Chem. Commun., 2016,52(46):7376-7379
[2] Pust P, Weiler V, Hecht C, et al. Nat. Mater., 2014,13(9):891-896
[3] Jiang G X, Yang B B, Zhao G Y, et al. Opt. Mater., 2018,83:93-98
[4] Guo Q F, Liao L B, Molokeev M S, et al. Mater. Res. Bull.,2015,72:245-251
[5] Feng L J, Tian Y, Wang L, et al. J. Mater. Sci., 2016,51(6):2841-2849
[6] Shang M M, Geng D L, Zhang Y, et al. J. Mater. Chem.,2012,22(36):19094-19104
[7] Lv Y, Jin Y H, Wang C L, et al. RSC Adv., 2017,7(69):43700-43707
[8] Guo Q F, Wang Q D, Jiang L W, et al. Phys. Chem. Chem.Phys., 2016,18(23):15545-15554
[9] Li G G, Zhao Y, Wei Y, et al. Chem. Commun., 2016,52(16):3376-3379
[10]Sokolnicki J, Zych E. J. Lumin., 2015,158:65-69
[11]Zhu G, Shi Y R, Mikami M, et al. Opt. Mater. Express,2013,3(2):229-236
[12]Que M D, Ci Z P, Wang Y H, et al. CrystEngComm, 2013,15(32):6389-6395
[13]Liu H K, Zhang Y Y, Liao L B, et al. J. Lumin., 2014,156:49-54
[14]Shang M M, Geng D L, Yang D M, et al. Inorg. Chem.,2013,52(6):3102-3112
[15]Fu L L, Fu Z L, Yu Y N, et al. Ceram. Int., 2015,41(5):7010-7016
[16]Li K, Geng D L, Shang M M, et al. J. Phys. Chem. C, 2014,118(20):11026-11034
[17]Wei L, Jia Y C, Lv W Z, et al. New J. Chem., 2013,37(11):3701-3705
[18]Li G G, Zhang Y, Geng D L, et al. ACS Appl. Mater.Interfaces, 2012,4(1):296-305
[19]Li G G, Geng D L, Shang M M, et al. J. Phys. Chem. C,2011,115(44):21882-21892
[20]Lee S H, Choi J I, Kim Y J, et al. Mater. Charact., 2015,103:162-169
[21]Kang Y C, Kim E J, Lee D Y, et al. J. Alloys Compd.,2002,347(1):266-270
[22]Tao Z X, Huang Y L, Seo H J. Dalton Trans., 2013,42(6):2121-2129
[23]White T J, Dong Z L. Acta Crystallogr. Sect. B:Struct. Sci.,2010,59(1):1-16
[24]Mathew M, Mayer I, Dickens B, et al. J. Solid State Chem.,1979,28(1):79-95
[25]Berry L G, Mason B, Dietrich R V. Mineralogy, Concepts,Descriptions, Determinations. San Francisco:W. H. Freeman,1983:550-551
[26]Han X M, Lin J, Xing R B, et al. J. Phys.:Condens. Matter,2003,15(12):2115-2126
[27]Liu H K, Luo Y, Mao Z Y, et al. J. Mater. Chem. C, 2014,2(9):1619-1627
[28]Zeng C, Liu H K, Hu Y M, et al. Opt. Laser Technol., 2015,74:6-10
[29]Jeon Y I, Bharat L K, Yu J S. J. Lumin., 2015,166:93-100
[30]Tang W J, Zhang F. Eur. J. Inorg. Chem., 2014(21):3387-3392
[31]Guan A X, Yao C Y, Wang G F, et al. J. Lumin., 2016,32(4):1-6
[32]Jin Y H, Lv Y, Hu Y H, et al. J. Lumin., 2017,185:106-111
[33]Ding X, Wang Y H. Phys. Chem. Chem. Phys., 2017,19(3):2449-2458
[34]Guo Y, Moon B K, Choi B C, et al. Ceram. Int., 2016,42(16):18324-18332
[35]Liang C, You H P, Fu Y B, et al. Optik, 2017,131:335-342
[36]Dexter D L, Schulman J H. J. Chem. Phys., 1954,22(6):1063-1070
[37]Hussain S K, Giang T T H, Yu J S. J. Alloys Compd., 2018,739:218-226
[38]YU Ting(于汀), GAO Ming-Yan(高明燕), SONG Yan(宋岩),et al. Chinese J. Inorg. Chem.(无机化学学报), 2018,34(5):857-863
[39]SUN Jia-Yue(孙家跃), DU Hai-Yan(杜海燕), HU WenXiang(胡文祥). Solid Luminous Materials(固体发光材料).Beijing:Chemical Industry Press, 2003.
[2] Pust P, Weiler V, Hecht C, et al. Nat. Mater., 2014,13(9):891-896
[3] Jiang G X, Yang B B, Zhao G Y, et al. Opt. Mater., 2018,83:93-98
[4] Guo Q F, Liao L B, Molokeev M S, et al. Mater. Res. Bull.,2015,72:245-251
[5] Feng L J, Tian Y, Wang L, et al. J. Mater. Sci., 2016,51(6):2841-2849
[6] Shang M M, Geng D L, Zhang Y, et al. J. Mater. Chem.,2012,22(36):19094-19104
[7] Lv Y, Jin Y H, Wang C L, et al. RSC Adv., 2017,7(69):43700-43707
[8] Guo Q F, Wang Q D, Jiang L W, et al. Phys. Chem. Chem.Phys., 2016,18(23):15545-15554
[9] Li G G, Zhao Y, Wei Y, et al. Chem. Commun., 2016,52(16):3376-3379
[10]Sokolnicki J, Zych E. J. Lumin., 2015,158:65-69
[11]Zhu G, Shi Y R, Mikami M, et al. Opt. Mater. Express,2013,3(2):229-236
[12]Que M D, Ci Z P, Wang Y H, et al. CrystEngComm, 2013,15(32):6389-6395
[13]Liu H K, Zhang Y Y, Liao L B, et al. J. Lumin., 2014,156:49-54
[14]Shang M M, Geng D L, Yang D M, et al. Inorg. Chem.,2013,52(6):3102-3112
[15]Fu L L, Fu Z L, Yu Y N, et al. Ceram. Int., 2015,41(5):7010-7016
[16]Li K, Geng D L, Shang M M, et al. J. Phys. Chem. C, 2014,118(20):11026-11034
[17]Wei L, Jia Y C, Lv W Z, et al. New J. Chem., 2013,37(11):3701-3705
[18]Li G G, Zhang Y, Geng D L, et al. ACS Appl. Mater.Interfaces, 2012,4(1):296-305
[19]Li G G, Geng D L, Shang M M, et al. J. Phys. Chem. C,2011,115(44):21882-21892
[20]Lee S H, Choi J I, Kim Y J, et al. Mater. Charact., 2015,103:162-169
[21]Kang Y C, Kim E J, Lee D Y, et al. J. Alloys Compd.,2002,347(1):266-270
[22]Tao Z X, Huang Y L, Seo H J. Dalton Trans., 2013,42(6):2121-2129
[23]White T J, Dong Z L. Acta Crystallogr. Sect. B:Struct. Sci.,2010,59(1):1-16
[24]Mathew M, Mayer I, Dickens B, et al. J. Solid State Chem.,1979,28(1):79-95
[25]Berry L G, Mason B, Dietrich R V. Mineralogy, Concepts,Descriptions, Determinations. San Francisco:W. H. Freeman,1983:550-551
[26]Han X M, Lin J, Xing R B, et al. J. Phys.:Condens. Matter,2003,15(12):2115-2126
[27]Liu H K, Luo Y, Mao Z Y, et al. J. Mater. Chem. C, 2014,2(9):1619-1627
[28]Zeng C, Liu H K, Hu Y M, et al. Opt. Laser Technol., 2015,74:6-10
[29]Jeon Y I, Bharat L K, Yu J S. J. Lumin., 2015,166:93-100
[30]Tang W J, Zhang F. Eur. J. Inorg. Chem., 2014(21):3387-3392
[31]Guan A X, Yao C Y, Wang G F, et al. J. Lumin., 2016,32(4):1-6
[32]Jin Y H, Lv Y, Hu Y H, et al. J. Lumin., 2017,185:106-111
[33]Ding X, Wang Y H. Phys. Chem. Chem. Phys., 2017,19(3):2449-2458
[34]Guo Y, Moon B K, Choi B C, et al. Ceram. Int., 2016,42(16):18324-18332
[35]Liang C, You H P, Fu Y B, et al. Optik, 2017,131:335-342
[36]Dexter D L, Schulman J H. J. Chem. Phys., 1954,22(6):1063-1070
[37]Hussain S K, Giang T T H, Yu J S. J. Alloys Compd., 2018,739:218-226
[38]YU Ting(于汀), GAO Ming-Yan(高明燕), SONG Yan(宋岩),et al. Chinese J. Inorg. Chem.(无机化学学报), 2018,34(5):857-863
[39]SUN Jia-Yue(孙家跃), DU Hai-Yan(杜海燕), HU WenXiang(胡文祥). Solid Luminous Materials(固体发光材料).Beijing:Chemical Industry Press, 2003.