真空紫外—紫外光子激发下某些离子的发光特性
摘要
本论文旨在研究在真空紫外和短波紫外光激发下，稀土离子
4f及5d电子跃迁的特点和发光机制，可能出现的能量传递和量
子剪裁的机制，影响发光性质的各种因素，探寻PDP、无汞荧
光灯等使用的荧光材料及其发光效率的途径。
本论文的研究内容包括以下几个方面：
1．研究在真空紫外和短波紫外光子激发下，Pr~(3+)离子及Eu~(3+)
离子的4f-4f及4f-5d能级电子跃迁，电荷迁移带及基质的激发
特点和发光机理，特别是Pr~(3+)的5d态的能量位置变化与Pr~(3+)的
发光性质的内在关联。
2．研究在硅酸盐和硼酸盐材料中，Pr~(3+)离子的紫外发射、光
子串级发射及Pr~(3+)和Gd~(3+)离子间的能量传递过程。
3．某些类汞离子和EU~(3+)掺杂发光材料的VUV光谱，以期了
解Bi~(3+)，Sb~(3+)离子的行为。
4．研究基质组成、晶体结构以及稀土离子所处的结晶学格
位对稀土离子发光性质及5d态能级位置的影响。
通过研究，本论文主要获得以下结论：
1．在几种碱土金属硅酸盐材料中，首次获得了Pr~(3+)的4f5d态
的紫外发射并实现了Pr~(3+)→Gd~(3+)的能量传递。研究表明，在共价
键较强的含Si-O四面体的材料中，Pr~(3+)的4f5d态位于~1S_0能级
之下，阳离子对其位置影响不大，难以产生Pr~(3+)的多光子串级
发射。
2．在La（BO_2）_3中，Pr~(3+)的4f5d态位于~1S_0能级之上，不仅
观察到了Pr~(3+)的串级发射，而且还存在基质的发射现象及Gd~(3+)
使Pr~(3+)的4f5d能级下降的现象。
3．在Eu~(3+)激活的硼酸盐中，首次观测到Bi~(3+)和Sb~(3+)离子对Eu~(3+)
的VUV激发光谱产生重大影响，可以有效地敏化Eu~(3+)的发光。
4．在硼磷酸盐中，Eu‘”在不同的晶体学格位上发光性质不
同。
The purpose of this paper is to research the spectroscopy
characteristics and the luminescent mechanisms of the electronic
transitions at 4f levels and 4f5d state of rare earths under VUV and
short wavelength ultraviolet exciting, the energy transfer and
quantum cutting, the reasons that infect luminescence properties,
and to find the methods of increasing the luminescent efficiency of
the PDP and the mercury-free lamps materials.
The content of this paper includes:
1. To study the characteristics and the luminescent mechanisms
of the 4f and 5d electronic transitions of Pr34 and Eu34 ions and the
charge transfer of Eu3+ ions under VUV and short wavelength
ultraviolet exciting.
2. To study the luminescent characteristic of Pr34 4f5d state,
photon cascade luminescence of Pr34.
3. To study the excitation spectra at VUV-UV of Bi34-Eu3+,
Sb34-Eu34 co-doped materials.
4. To study the affection of the host constitution, the crystal
structure and the rare earth lattices to the rare earth luminescent
properties and the location of the 5d energy levels.
The results and progresses obtained are as follows:
1. In several alkali-earth silicate host, the emission of Pr34
4f5d state and the Pr3+Gd34 energy transfer were observed, the
cascade emission of Pr3+ can not be obtained.
2. The photon cascade of Pr34 in La(B 02)3 was obtained and the
host emission was observed, the 4f5d energy level decreased when
doped with Gd34.
3. In + activated Ln(B0j3 (Ln=La, Gd), Sb34 ions and Bi34
ions affected the absorptive properties at VUV and UV.
4. In Eu34 activated Ln706(B03)(P04)2 (Ln=La, Gd) ,the
luminescent properties was different when Eu34 ions were at
different lattices.
In this paper, the luminescent properties of Pr34 and Eu34 under
VUV and short wavelength UV excited were studied. At present,
the luminescent materials under VUV exciting were widely studied,
and this kind of materials have great potential at FED, PDP and
mercury-free lamps. The results of this paper have added the new
contents to this region, a new method was obtained about how to
increase the absorptive intensities at VUV of the samples, and the
Eu34 activated Ln706(B03)(P04)2 have applying value to some
extent.
4f及5d电子跃迁的特点和发光机制，可能出现的能量传递和量
子剪裁的机制，影响发光性质的各种因素，探寻PDP、无汞荧
光灯等使用的荧光材料及其发光效率的途径。
本论文的研究内容包括以下几个方面：
1．研究在真空紫外和短波紫外光子激发下，Pr~(3+)离子及Eu~(3+)
离子的4f-4f及4f-5d能级电子跃迁，电荷迁移带及基质的激发
特点和发光机理，特别是Pr~(3+)的5d态的能量位置变化与Pr~(3+)的
发光性质的内在关联。
2．研究在硅酸盐和硼酸盐材料中，Pr~(3+)离子的紫外发射、光
子串级发射及Pr~(3+)和Gd~(3+)离子间的能量传递过程。
3．某些类汞离子和EU~(3+)掺杂发光材料的VUV光谱，以期了
解Bi~(3+)，Sb~(3+)离子的行为。
4．研究基质组成、晶体结构以及稀土离子所处的结晶学格
位对稀土离子发光性质及5d态能级位置的影响。
通过研究，本论文主要获得以下结论：
1．在几种碱土金属硅酸盐材料中，首次获得了Pr~(3+)的4f5d态
的紫外发射并实现了Pr~(3+)→Gd~(3+)的能量传递。研究表明，在共价
键较强的含Si-O四面体的材料中，Pr~(3+)的4f5d态位于~1S_0能级
之下，阳离子对其位置影响不大，难以产生Pr~(3+)的多光子串级
发射。
2．在La（BO_2）_3中，Pr~(3+)的4f5d态位于~1S_0能级之上，不仅
观察到了Pr~(3+)的串级发射，而且还存在基质的发射现象及Gd~(3+)
使Pr~(3+)的4f5d能级下降的现象。
3．在Eu~(3+)激活的硼酸盐中，首次观测到Bi~(3+)和Sb~(3+)离子对Eu~(3+)
的VUV激发光谱产生重大影响，可以有效地敏化Eu~(3+)的发光。
4．在硼磷酸盐中，Eu‘”在不同的晶体学格位上发光性质不
同。
The purpose of this paper is to research the spectroscopy
characteristics and the luminescent mechanisms of the electronic
transitions at 4f levels and 4f5d state of rare earths under VUV and
short wavelength ultraviolet exciting, the energy transfer and
quantum cutting, the reasons that infect luminescence properties,
and to find the methods of increasing the luminescent efficiency of
the PDP and the mercury-free lamps materials.
The content of this paper includes:
1. To study the characteristics and the luminescent mechanisms
of the 4f and 5d electronic transitions of Pr34 and Eu34 ions and the
charge transfer of Eu3+ ions under VUV and short wavelength
ultraviolet exciting.
2. To study the luminescent characteristic of Pr34 4f5d state,
photon cascade luminescence of Pr34.
3. To study the excitation spectra at VUV-UV of Bi34-Eu3+,
Sb34-Eu34 co-doped materials.
4. To study the affection of the host constitution, the crystal
structure and the rare earth lattices to the rare earth luminescent
properties and the location of the 5d energy levels.
The results and progresses obtained are as follows:
1. In several alkali-earth silicate host, the emission of Pr34
4f5d state and the Pr3+Gd34 energy transfer were observed, the
cascade emission of Pr3+ can not be obtained.
2. The photon cascade of Pr34 in La(B 02)3 was obtained and the
host emission was observed, the 4f5d energy level decreased when
doped with Gd34.
3. In + activated Ln(B0j3 (Ln=La, Gd), Sb34 ions and Bi34
ions affected the absorptive properties at VUV and UV.
4. In Eu34 activated Ln706(B03)(P04)2 (Ln=La, Gd) ,the
luminescent properties was different when Eu34 ions were at
different lattices.
In this paper, the luminescent properties of Pr34 and Eu34 under
VUV and short wavelength UV excited were studied. At present,
the luminescent materials under VUV exciting were widely studied,
and this kind of materials have great potential at FED, PDP and
mercury-free lamps. The results of this paper have added the new
contents to this region, a new method was obtained about how to
increase the absorptive intensities at VUV of the samples, and the
Eu34 activated Ln706(B03)(P04)2 have applying value to some
extent.
引文
1． Dieke, G. H. 1961, Spectroscopic Observations on Maser Materials, in: Advances in Quantum Electronics, ed. J.R. Singer, Columbia University Press, New York., 1968．
2． L. R. Elias, Wm. S. Heaps, and W. M. Yen, Excitation of uv fluorescence in LaF3 doped with trivalent cerium and praseodymium, Physical Review B, 1973, B8(11) : 4989-4995．
3． Wm. S. Heaps, L. R. Elias, and W. M. Yen, Vacuum-ultraviolet absorption bands of trivalent lanthanides in LaF3, Physical Review B, 1976, B13: 94．
4． K. H. Yang and J. A. Deluca, VUV fluorescence pf Nd3+-, Er3+-, and Tm3+-doped trifluorides and tunable coherent sources from 1650 to 2600A, Applied Physics Letters, 1976, 29(8) : 499-501．
5． K. H. Yang and J. A. Deluca, Energy transfer between 5d electronic states of trivalent rare-earth ions, Appl. Phys. Lett. 1979, 35(4) : 301-302．
6． E. Sarantopoulou, Z. Kollia, A. C. Cefalas, M. A. Dubinskii, and C. A. Nicolaides, Vacuum ultraviolet and ultraviolet fluorescence and absorption studies of Er3+-doped LiLuF4 single crystals, Appl. Phys. Lett. 1994, 65(7) : 813-815．
7． R. T. Wegh, H. Donker, and A. Mei jerink, Spin-allowed and spin-forbidden fd emission from Er3+ and LiYF4, Physical Review B, 1998, 57(4) : R2025-R2028．
8． J.Becker, J. Y. Gesland, N. Yu. Kirikova, etc. VUV emission of Er3+ and Tm3+ in fluoeide crystals, Journal of Luminescence, 1998, 78: 91-96．
9． R.T. Wegh, H.Donker, and A. Meijerink, Vacuum-ultraviolet spectroscopy and quantum cutting for Gd3+ in LiYF4 Physical
10.Ren(?) T. Wegh, Andries Meijerink, Ralf-Johan Lamminm(?)ki, Jorma H(?)ls(?), Extending Dieke's diagram, Journal of Luminescence, 2000, 87-89: 1002-1004.
11.C.J. Summers, SID 1997, Seminar Lectrue Notes, Vol. 1, M-5.
12.H. Donker, R.T. Weigh, A. Meijerink, J.C. Krupa, M. Queffelec, New concepts for VUV phosphoors with high quantum efficiency (q＞100%). J. SID, 1998, 6(1): 73-76.
13.S.M. Jacobsen, J. SID, 1996, 4(4): 331
14.Jurno Koike, Takehiro Kojima, and Ryuya Toyonaga, New tricolor phosphors for gas discharge display, J. Electrochem. Soc., 1979, 126(6): 1008-1010.
15．刘行仁，王晓君，申五福，全色等离子体平板显示器用发光材料，发光快报，1995，3：9。
16.S. Mikoshiba, Color Plasma Displays, 1998SID, Seminar Lecture Notes, Voll: M-4/3, Anaheim, CA, 1998.
17.A.Mayolet, J.C.Krupa, J.Gerard and P. Martion, Luminescence of Eu~(3+) doped materials excited by VUV synchrotron radiation, Materials Chemistry and Physics, 1992, 31: 107-100.
18.E.Nakazawa and F. Shiga, Vacuum ultraviolet luminescence excitation spectra of RPO_4: Eu~(3+) (R= Y, La, Gd and Lu), Journal of Luminescence, 1977, 15: 255-259.
19.T.J Popma, W.F. van der Weg and K. Thimm, Journal of luminescence, 1981, 24&25: 289.
20.J.K.Berkowitz and J.A.Olsen, Investigation of luminescent materials under ultraviolet excitation energies from 5 to 25 eV, Journal of luminescence, 1991, 50: 111-121.
21.Visible quantum cutting in LiGdF_4: Eu through downconversion, Science, 1999, 283: 663-666.
22．刘行仁，稀土发光材料有其应用的世纪回顾和前瞻，中国稀土学会《稀土》杂志编辑部，2001年月1月，p15．
23．刘行仁等，PDP、FED及LED用发光材料的最新进展——'98全国平板显示会议邀请报告，液晶与显示，1998，13(3)：155-161。
24．王晓君，刘行仁，申五福，真空紫外光激励的绿色荧光粉的研究，光电子·激光，1995，6：266-268。
25．余宪恩，肖勇强，真空紫外荧光粉 BaAl_(12)O_(19)：Mn~(2+)和 BaMg_2Al_(12)O_(21)：Eu~(2+)Mn~(2+)绿粉的研制，中国稀土学报，1998，16：1117-1119。
26.P. Dorenbos, M.Marsman, C.W.E.Van Eijk, M.V.Korzhik and B.I.Minkov, Scintillation properties of Y_2SiO_5 crystals, Radiation Effects and Defects in Solids, 1995, 135: 325-328.
27.M.L.Meilman, A.I.Kolomiitsev, A.M.Kevorkov, and Kh.S.Bagdasarov, Ultraviolet luminescence in interconfigurational electronic transitions in praseodymium-activated YAG crystals, Opt. Spectrosc. (USSR)1984, 57(2): 145-146.
28.G.Blasse, J.P.M.van Vliet, J.W.M.Verwey, R.Hoogendam and M.Wiegel, Luminescence of Pr~(3+) in scandium borate (ScBO_3) and the host lattice dependence of the Stokes shift, J. Phys. Chem. Solids. 1989, 50(6): 583-585.
29.R.C.Naik, N.P. Kranjikar and N.A.Narasimham, X-ray excited optical luminescence spectrum of Pr-doped YPO_4, Solid State Communications, 1981, 38:389-391.
30.J.Th.W. de Hair, The luminescence of Pr~(3+) in BaY_4Si_5O_(17), Journal of Solid State Chemistry, 1980, 33:33-36。
2． L. R. Elias, Wm. S. Heaps, and W. M. Yen, Excitation of uv fluorescence in LaF3 doped with trivalent cerium and praseodymium, Physical Review B, 1973, B8(11) : 4989-4995．
3． Wm. S. Heaps, L. R. Elias, and W. M. Yen, Vacuum-ultraviolet absorption bands of trivalent lanthanides in LaF3, Physical Review B, 1976, B13: 94．
4． K. H. Yang and J. A. Deluca, VUV fluorescence pf Nd3+-, Er3+-, and Tm3+-doped trifluorides and tunable coherent sources from 1650 to 2600A, Applied Physics Letters, 1976, 29(8) : 499-501．
5． K. H. Yang and J. A. Deluca, Energy transfer between 5d electronic states of trivalent rare-earth ions, Appl. Phys. Lett. 1979, 35(4) : 301-302．
6． E. Sarantopoulou, Z. Kollia, A. C. Cefalas, M. A. Dubinskii, and C. A. Nicolaides, Vacuum ultraviolet and ultraviolet fluorescence and absorption studies of Er3+-doped LiLuF4 single crystals, Appl. Phys. Lett. 1994, 65(7) : 813-815．
7． R. T. Wegh, H. Donker, and A. Mei jerink, Spin-allowed and spin-forbidden fd emission from Er3+ and LiYF4, Physical Review B, 1998, 57(4) : R2025-R2028．
8． J.Becker, J. Y. Gesland, N. Yu. Kirikova, etc. VUV emission of Er3+ and Tm3+ in fluoeide crystals, Journal of Luminescence, 1998, 78: 91-96．
9． R.T. Wegh, H.Donker, and A. Meijerink, Vacuum-ultraviolet spectroscopy and quantum cutting for Gd3+ in LiYF4 Physical
10.Ren(?) T. Wegh, Andries Meijerink, Ralf-Johan Lamminm(?)ki, Jorma H(?)ls(?), Extending Dieke's diagram, Journal of Luminescence, 2000, 87-89: 1002-1004.
11.C.J. Summers, SID 1997, Seminar Lectrue Notes, Vol. 1, M-5.
12.H. Donker, R.T. Weigh, A. Meijerink, J.C. Krupa, M. Queffelec, New concepts for VUV phosphoors with high quantum efficiency (q＞100%). J. SID, 1998, 6(1): 73-76.
13.S.M. Jacobsen, J. SID, 1996, 4(4): 331
14.Jurno Koike, Takehiro Kojima, and Ryuya Toyonaga, New tricolor phosphors for gas discharge display, J. Electrochem. Soc., 1979, 126(6): 1008-1010.
15．刘行仁，王晓君，申五福，全色等离子体平板显示器用发光材料，发光快报，1995，3：9。
16.S. Mikoshiba, Color Plasma Displays, 1998SID, Seminar Lecture Notes, Voll: M-4/3, Anaheim, CA, 1998.
17.A.Mayolet, J.C.Krupa, J.Gerard and P. Martion, Luminescence of Eu~(3+) doped materials excited by VUV synchrotron radiation, Materials Chemistry and Physics, 1992, 31: 107-100.
18.E.Nakazawa and F. Shiga, Vacuum ultraviolet luminescence excitation spectra of RPO_4: Eu~(3+) (R= Y, La, Gd and Lu), Journal of Luminescence, 1977, 15: 255-259.
19.T.J Popma, W.F. van der Weg and K. Thimm, Journal of luminescence, 1981, 24&25: 289.
20.J.K.Berkowitz and J.A.Olsen, Investigation of luminescent materials under ultraviolet excitation energies from 5 to 25 eV, Journal of luminescence, 1991, 50: 111-121.
21.Visible quantum cutting in LiGdF_4: Eu through downconversion, Science, 1999, 283: 663-666.
22．刘行仁，稀土发光材料有其应用的世纪回顾和前瞻，中国稀土学会《稀土》杂志编辑部，2001年月1月，p15．
23．刘行仁等，PDP、FED及LED用发光材料的最新进展——'98全国平板显示会议邀请报告，液晶与显示，1998，13(3)：155-161。
24．王晓君，刘行仁，申五福，真空紫外光激励的绿色荧光粉的研究，光电子·激光，1995，6：266-268。
25．余宪恩，肖勇强，真空紫外荧光粉 BaAl_(12)O_(19)：Mn~(2+)和 BaMg_2Al_(12)O_(21)：Eu~(2+)Mn~(2+)绿粉的研制，中国稀土学报，1998，16：1117-1119。
26.P. Dorenbos, M.Marsman, C.W.E.Van Eijk, M.V.Korzhik and B.I.Minkov, Scintillation properties of Y_2SiO_5 crystals, Radiation Effects and Defects in Solids, 1995, 135: 325-328.
27.M.L.Meilman, A.I.Kolomiitsev, A.M.Kevorkov, and Kh.S.Bagdasarov, Ultraviolet luminescence in interconfigurational electronic transitions in praseodymium-activated YAG crystals, Opt. Spectrosc. (USSR)1984, 57(2): 145-146.
28.G.Blasse, J.P.M.van Vliet, J.W.M.Verwey, R.Hoogendam and M.Wiegel, Luminescence of Pr~(3+) in scandium borate (ScBO_3) and the host lattice dependence of the Stokes shift, J. Phys. Chem. Solids. 1989, 50(6): 583-585.
29.R.C.Naik, N.P. Kranjikar and N.A.Narasimham, X-ray excited optical luminescence spectrum of Pr-doped YPO_4, Solid State Communications, 1981, 38:389-391.
30.J.Th.W. de Hair, The luminescence of Pr~(3+) in BaY_4Si_5O_(17), Journal of Solid State Chemistry, 1980, 33:33-36。