PWG玻璃陶瓷中的局域效应研究
摘要
半导体激光器泵浦的可见光上转换激光器的研究对光电子器件的
发展具有重要的意义。掺杂稀土离子的PWG是一种具重要意义的发光
上转换材料，它从红外到紫外波长范围内具有极高的透明度，这种材
料容易制备成光纤以便在光电子领域获得更大的应用。与材料的结构
和声子紧密相关的上转换效率的提高是这方面研究主要问题之一。晶
格振动和声子的问题是这个工作和所有固体领域都必须考虑的问题，
因而也几乎在固体物理的所有领域中起着重要而基本的作用。
本文借助于喇曼光散射技术研究了稀土掺杂和末掺杂PWG中的局
域效应及其在这类材料中的重要作用。研究获得的主要如下结果：
1．Yb~（3+）和 Tm~（3+）离子替代了部分Yb~（2+）离子格位而形成了正电荷局域杂
质中心，PWG：Yb~（3+）、Tm~（3+）中的这些局域杂质中心形成的局域电塌使PWG：
Yb~（3+）、Yb~（3+）Tm具有很强的晶向有序微晶结构；除了晶格振动对极化率调
制引起的喇曼散射外，这种局域电塌诱发了新的附加喇曼散射效应；
研究发现：在适当掺杂的浓度下，只有在局域化的Yb~（3+）和Tm~（3+）离子的
共协作用下才能便PWG中的所有振动模窄化。这个结果对功能材料的
制备和性能的提高具有重要的理论指导意义。
2．通过水分子与微晶中某些基团相互作用的实验研究，提出了通过
水分子对PWG中某些基团化学键的扰动可定性地确定基团的维度结构
物理方法。
3．从得到 PWG：Yb~（3+）、Tm~（3+）的喇曼光谱强度与温度的函数关系发现
4~#PWG：Yb~（3+）、Tm~（3+）玻璃陶瓷具有铁电性并在315吐℃附近开始表现出抗
铁电性，即开始从有序到无序的相变；高压诱导相变结果表明：与局
域化的Yb~（3+）和Tm~（3+）离子有关的结构是不具有可压缩性。
PA：6320P；4270C
Studies of red to b1ue up--conversion 1aser pumped by red
semiconductor 1aser are important for the deve1opments of
photo--e1ectronics. PWG g1ass ceramics doped with rare-
earth ions are attract ive because they are good up--conversion
. -
luminescence materla1s. In addition, they show a high
transparency from the UV to the IR and relative1y
concentrat ions of triva1ent rare earth ions can be introduced
into the matrices. This kind of materia1s can be used into
some important fie1ds of photo--e1ectronics on future, 0ne of
studied prob1ems is main1y focused on deve1opment of
.
luminescence efficiency assoc iated with phonon and the
structure of the host. These prob1ems of matrices vibration
and phone must be thought for this fie1d and all so1id fie1ds
,
witch act on some importance on a11 fie1ds of solid physics.
Some propert ies of 1ocated modes have are studied in PWG
g1ass ceramics doped and undoped by Yb3+ and Tm3+ions by Raman
spectra. Fo1lowing by these main resu1ts:
1. It was found that 1ocated e1ectric fie1d is generated after
Ybs+and Tm3+ions are doped into PWG, witch resu1ts in a
consistence of crysta11ine direct ions of microcrysta1 in
PWG. The co--operation of Yb3+and Tm3+ ions makes Raman
.
vibrationa1 modes from PWG to narrow with special
c o nc e nt rat i o n.
2. The interactions of W03 in PWG with water indicate that the
W0a unit has a stab1e three--dimension structure.
3. A new phase transition of 4#PWG: Yb'+, Tm3+ of an order--disorder.
type, at hi gh temperature about 315'C, was found. Moreover,
Qn the basis of the temperature dependence of Raman intensity,
. t
a compari son was made with respect to PWG undoped: It was found
that these structura1 uni ts associated wi th Yb3+ and Tm3+are
1ack of the anoma1ous compress ibi 1 ity.
发展具有重要的意义。掺杂稀土离子的PWG是一种具重要意义的发光
上转换材料，它从红外到紫外波长范围内具有极高的透明度，这种材
料容易制备成光纤以便在光电子领域获得更大的应用。与材料的结构
和声子紧密相关的上转换效率的提高是这方面研究主要问题之一。晶
格振动和声子的问题是这个工作和所有固体领域都必须考虑的问题，
因而也几乎在固体物理的所有领域中起着重要而基本的作用。
本文借助于喇曼光散射技术研究了稀土掺杂和末掺杂PWG中的局
域效应及其在这类材料中的重要作用。研究获得的主要如下结果：
1．Yb~（3+）和 Tm~（3+）离子替代了部分Yb~（2+）离子格位而形成了正电荷局域杂
质中心，PWG：Yb~（3+）、Tm~（3+）中的这些局域杂质中心形成的局域电塌使PWG：
Yb~（3+）、Yb~（3+）Tm具有很强的晶向有序微晶结构；除了晶格振动对极化率调
制引起的喇曼散射外，这种局域电塌诱发了新的附加喇曼散射效应；
研究发现：在适当掺杂的浓度下，只有在局域化的Yb~（3+）和Tm~（3+）离子的
共协作用下才能便PWG中的所有振动模窄化。这个结果对功能材料的
制备和性能的提高具有重要的理论指导意义。
2．通过水分子与微晶中某些基团相互作用的实验研究，提出了通过
水分子对PWG中某些基团化学键的扰动可定性地确定基团的维度结构
物理方法。
3．从得到 PWG：Yb~（3+）、Tm~（3+）的喇曼光谱强度与温度的函数关系发现
4~#PWG：Yb~（3+）、Tm~（3+）玻璃陶瓷具有铁电性并在315吐℃附近开始表现出抗
铁电性，即开始从有序到无序的相变；高压诱导相变结果表明：与局
域化的Yb~（3+）和Tm~（3+）离子有关的结构是不具有可压缩性。
PA：6320P；4270C
Studies of red to b1ue up--conversion 1aser pumped by red
semiconductor 1aser are important for the deve1opments of
photo--e1ectronics. PWG g1ass ceramics doped with rare-
earth ions are attract ive because they are good up--conversion
. -
luminescence materla1s. In addition, they show a high
transparency from the UV to the IR and relative1y
concentrat ions of triva1ent rare earth ions can be introduced
into the matrices. This kind of materia1s can be used into
some important fie1ds of photo--e1ectronics on future, 0ne of
studied prob1ems is main1y focused on deve1opment of
.
luminescence efficiency assoc iated with phonon and the
structure of the host. These prob1ems of matrices vibration
and phone must be thought for this fie1d and all so1id fie1ds
,
witch act on some importance on a11 fie1ds of solid physics.
Some propert ies of 1ocated modes have are studied in PWG
g1ass ceramics doped and undoped by Yb3+ and Tm3+ions by Raman
spectra. Fo1lowing by these main resu1ts:
1. It was found that 1ocated e1ectric fie1d is generated after
Ybs+and Tm3+ions are doped into PWG, witch resu1ts in a
consistence of crysta11ine direct ions of microcrysta1 in
PWG. The co--operation of Yb3+and Tm3+ ions makes Raman
.
vibrationa1 modes from PWG to narrow with special
c o nc e nt rat i o n.
2. The interactions of W03 in PWG with water indicate that the
W0a unit has a stab1e three--dimension structure.
3. A new phase transition of 4#PWG: Yb'+, Tm3+ of an order--disorder.
type, at hi gh temperature about 315'C, was found. Moreover,
Qn the basis of the temperature dependence of Raman intensity,
. t
a compari son was made with respect to PWG undoped: It was found
that these structura1 uni ts associated wi th Yb3+ and Tm3+are
1ack of the anoma1ous compress ibi 1 ity.
引文
[1] W. Xu, J.P.Denis, G. Ozen, A. Kermaoui, F. Pelle, J. Appl. Phys. 75 (8) , 4180(1994) .
[2] W. Xu, J, P. Denis, G. Ozen, A. Kermaoui, Phys. stat. sol. (a) 141, 445 (1994)
[3] H. Verwei j, J. H. J. M. buster, J. Non-Cryst. Solids34, 81 (1979) . S. J. Ribeiro, J. Dexpert-Ghys, B. Piriou, V. R. Mastelaro, J. Non-Cryst. Solids 159, 213 (1993) .
[4] S. J. Ribeiro, J. Dexper-Ghys, B. Piriou, J. Non-Cryst. Solids 159, 213(1993)
[5] Annapoorna A. kella, Elizabeth A. Downing, Lambertus Hesselink, Journal of Non-Ctystalline Solids 213& 214, 1(1997) .
[6] G . Schafer, J. Phys. Chem. Solids, 12 (1960) 233．
[7] D.Baldassare and R.C.Powell, Phonons and Resonance in Solids, John Wiley & Sons, Inc., 1982, ?.6．
[8] A. S. Barker, A. J. Sievers, Rev. of ModernPhys. , 47, Suppl. No. 2(1990) S_1．
[9] T.M. Haridasan ect, Phys. Rev. , B20 (1994) 3462．
[10] Y. Farger and M. P. Fontana, Electronic and Vibrational Properties of Point Defects in Ionic Crystal, Amsterdam, Netherland, North Holland,(1989) .
[11] P. A. Aannested and E. M. Pucell, in Anuual Rev. of Astronomy and Astrophys. ,ed. By L. Goldberg, Palo Alto 11(1991) 309．
[12] Terutaro Nakammura, Masaaki Takashige, Hikaru Terauchi, W. N. Lawless. Japenese Journal of Appled Physics. Vol.23, No. 10, (1984) 1265．
[13] R. F. Walls and A. A. Maradudin, Prog. Thero. Phys. , 24, (1981) 1055．
[14] F. E. A. Melo, J. Mendes Filho and J. E. Moreira, Journal of Raman Spectroscopy, Vol 15,No.2, 128 (1984) .
[2] W. Xu, J, P. Denis, G. Ozen, A. Kermaoui, Phys. stat. sol. (a) 141, 445 (1994)
[3] H. Verwei j, J. H. J. M. buster, J. Non-Cryst. Solids34, 81 (1979) . S. J. Ribeiro, J. Dexpert-Ghys, B. Piriou, V. R. Mastelaro, J. Non-Cryst. Solids 159, 213 (1993) .
[4] S. J. Ribeiro, J. Dexper-Ghys, B. Piriou, J. Non-Cryst. Solids 159, 213(1993)
[5] Annapoorna A. kella, Elizabeth A. Downing, Lambertus Hesselink, Journal of Non-Ctystalline Solids 213& 214, 1(1997) .
[6] G . Schafer, J. Phys. Chem. Solids, 12 (1960) 233．
[7] D.Baldassare and R.C.Powell, Phonons and Resonance in Solids, John Wiley & Sons, Inc., 1982, ?.6．
[8] A. S. Barker, A. J. Sievers, Rev. of ModernPhys. , 47, Suppl. No. 2(1990) S_1．
[9] T.M. Haridasan ect, Phys. Rev. , B20 (1994) 3462．
[10] Y. Farger and M. P. Fontana, Electronic and Vibrational Properties of Point Defects in Ionic Crystal, Amsterdam, Netherland, North Holland,(1989) .
[11] P. A. Aannested and E. M. Pucell, in Anuual Rev. of Astronomy and Astrophys. ,ed. By L. Goldberg, Palo Alto 11(1991) 309．
[12] Terutaro Nakammura, Masaaki Takashige, Hikaru Terauchi, W. N. Lawless. Japenese Journal of Appled Physics. Vol.23, No. 10, (1984) 1265．
[13] R. F. Walls and A. A. Maradudin, Prog. Thero. Phys. , 24, (1981) 1055．
[14] F. E. A. Melo, J. Mendes Filho and J. E. Moreira, Journal of Raman Spectroscopy, Vol 15,No.2, 128 (1984) .