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LUMINESCENCE IN POTENTIAL FLUORIDE GLASS LASERS
C. Jørgensen
To cite this version:
C. Jørgensen. LUMINESCENCE IN POTENTIAL FLUORIDE GLASS LASERS. Journal de
Physique Colloques, 1987, 48 (C7), pp.C7-447-C7-450. �10.1051/jphyscol:19877106�. �jpa-00226922�
JOURNAL DE PHYSIQUE
C o l l o q u e C7, s u p p l b m e n t a u n 0 1 2 , Tome 4 8 , dBcembre 1 9 8 7
LUMINESCENCE IN POTENTIAL FLUORIDE GLASS LASERS
Section d e Chimie, Universite de Geneve, 30, Quai Ansermet, CH-1211 Geneve 4 , Switzerland
A b s t r a c t
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F l u o r i d e g l a s s e s o f t h e z i r c o n i u m b a r i u m l a n t h a n i d e t y p e ( i n v e n t e d R e n n e s , 1 9 7 5 ) a n d l e a d g a l l i u m z i n c ( o r m a n g a n e s e ) t y p e ( i n v e n t e d Le Mans, 1 9 7 9 ) show l u m i n e s c e n c e of l a n t h a n i d e J- L e v e l s s i t u a t e d a t l e a s t 2000 c m - ' a b o v e t h e c l o s e s t l o w e r l e v e l( t h i s l i m i t i s a f e w t i m e s l a r g e r i n m o s t o t h e r m a t e r i a l s ) . N o t o n l y i s t h e n o n - r a d i a t i v e d e - e x c i t a t i o n a s weak a s i n c r y s t a l l i n e LaF3 ( s t u d i e d by Weber) b u t e n e r g y t r a n s f e r b e t w e e n neodymium a n d y t t e r b i u m ( I I I ) , o r f r o m m a n g a n e s e ( I I ) , a n d t o some e x t e n t f r o m c h r o m i u m ( I I I ) , t o l u m i n e s c e n t J - l e v e l s o f n e o d y m i u m ( I I I ) ,
e r b i u m ( I I 1 ) a n d t h u l i u m ( I I 1 ) i s h i g h l y e f f i c i e n t e v e n a t low c o n c e n t r a t i o n s . O n e a d v a n t a g e f o r l a s e r a p p l i c a t i o n s i s t h a t t h e l o w e s t q u a r t e t s t a t e o f m a n g a n e s e ( I 1 ) h a s a l i f e - t i m e 10 t o 1 5 m i l l i s e c o n d s ( l i k e i n many p h o s p h a t e g l a s s e s a n d c r y s t a l l i n e compounds) a l l o w i n g e n e r g y t r a n s f e r , e x t e n d i n g by h u g e f a c t o r s t h e a v e r a g e l i f e - t i m e o f t h e e m i t t i n g J - 1 e v e l s . T h o u g h t h e t e r a - w a t t l a s e r s (Livermore,California,1978) i n d u c i n g d e u t e r i u m - t r i t i u m f u s i o n a r e s i l i c a t e g l a s s c o n t a i n i n g n e o d y m i u m ( I I 1 )
,
f l u o r i d e g l a s s e s s h o u l d b e p r e f e r a b l e f o r many p u r p o s e s . T h e e v a l u a t i o n o f l a s e r p a r a m e t e r s from s m a l l - s c a l e e x p e r i m e n t a t i o n i s f e a s i b l e .
One n e c e s s a r y c o n d i t i o n f o r l a s e r a c t i o n i s p o p u l a t i o n i n v e r s i o n . F u r t h e r o n , t h e m u l t i f a r i o u s p r o c e s s e s o f n o n - r a d i a t i v e d e - e x c i t a t i o n may d e c r e a s e t h e quantum y i e l d o f l u m i n e s c e n c e t o a n e x t e n t i m p a i - r i n g l a s e r a c t i o n [ l ] . G a s e o u s a t o m s , a n d l u m i n e s c e n t s p e c i e s i n w a t e r a n d o t h e r s o l v e n t s o f low v i s c o s i t y , h a v e a l a r g e p a r t o f t h e non- r a d i a t i v e d e a c t i v a t i o n ( i n c l u d i n g p h o t o c h e m i c a l r e a c t i o n s ) i n d u c e d by c o l l i s i o n s . I n h i g h - v i s c o s i t y v i t r e o u s m a t e r i a l s [ 2 1 a n d i n s o l i d s , t h e c o l l i s i o n s p l a y n o r 6 1 e r b u t W e b e r [ 3 ] f o u n d t h a t e x c i t e d J - l e v e l s o f t r i v a l e n t l a n t h a n i d e s i n c o r p o r a t e d i n c r y s t a l l i n e LaF3 a n d Y203 show a r a t e o f m u l t i - p h o n o n d e - e x c i t a t i o n W = B e x p [ -
a(&)
1 w h e r e &( h a v i n g t h e d i m e n s i o n o f a r e c i p r o c a l e n e r g y ) m u l t i p l i e s t h e e n e r g y g a p
A E
b e t w e e n t h e e m i t t i n g J - l e v e l a n d t h e c l o s e s t l o w e r J - l e v e l . A c l o s e r a n a l y s i s [ 4 , 5 ] s u g g e s t s t o r e w r i t e.
,l o g l o ~ * = l o g B
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0 . 8 6 0 ~ % 0 = l o g l O B-
( 0 . 8 6 / a ) 10a l s o a p p l i c a b l e t o g l a s s e s [ l , 2 ] a n d s o l u t i o n s . T h e c h a r a c t e r i s t i c phonon e n e r g y
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i s t h e h i g h e s t v i b r a t i o n a l n o r m a l mode o f a p o l y - a t o m i c s p e c i e s , o r t h e h i g h e s t f r e q u e n c y i n . a c r y s t a l . T h e s m a l l c o n s t a n t a i n t h e d e f i n i t i o n a%&)= ( I / C C ) i s 0 . 4 f o r H20 a n d D20 a q u a i o n s , v a r i e s i n c r y s t a l s f r o m 0.25 i n L a c 1 t o 0 . 5 i n Y203,and i s t y p i c a l l y 0 . 2 t o 0 . 5 i n g l a s s e s . T h e Weber t r e a 2 m e n t o f m u l t l - p h o n o n r e l a x a t i o n i s i n d e p e n d e n t o f t h e l a n t h a n i d e c o n s i d e r e d , i n c o n t r a s t t o t h e J u d d - O f e l t t h e o r y f o r r a d i a t i v e t r a n s i t i o n p r o b a b i l i t i e s b e t w e e n J - l e v e l sArticle published online by EDP Sciences and available at http://dx.doi.org/10.1051/jphyscol:19877106
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[ 1 , 2 , 6 - 8 1 i n v o l v i n g t h r e e s q u a r e d m a t r i x e l e m e n t s U, ( t = 2 , 4 , 6 ) d e t e r - m i n e d b y e l e c t r i c ~ ~ - ~ o l a r t r a n s i t i o n s b e t w e e n t w o i i v e n J - l e v e l s t a n d t h r e e m a t e r i a l p a r a m e t e r s Q r a t h e r c o m p a r a b l e t o M h e r e , t h o u g h t h e y v a r y w i t h t h e l a n t h a n i d e . t ~ o r o u r p , u r p o s e s , t h e J u d d - O f e l t p a r a m e t - r i z a t i o n i s i m p o r t a n t b y t r e a t i n g s i m u l t a n e o u s l y a b s o r p t i o n b a n d i n t e n s i t i e s ( f r o m w h i c h Q a r e e v a l u a t e d f r o m e x p e r i m e n t a l l y o v e r - d e t e r m i n e d sums U
9
) a n 5 r a d i a t i v e p r o b a b i l i t i e s . E v e n when t h e p r o b a b i l i t y x o f t n o n - r a d i a t i v e d e - e x c i t a t i o n t i s v e r y c l o s e t o 1 , t h e b r a n c h i n g r a t i o s o f l u m i n e s c e n c e f r o m a g i v e n l e v e l t o s e v e r a l l o w e r l e v e l s r e m a i n t h e s a m e , w i t h a l l t h e r a d i a t i v e7
m u l t i p l i e d by ( 1 - x ) . Many s o l i d - s t a e l a s e r s u s e t h e t r a n s i t i o n f r o m 4~ t o t h e f i r s t e x c i t e d l e v e l 'Il i 2 o f neodymium (111) i n t h e g a r n ~ i 2 ~ d x ~ 3 - x ~ 1 5 0 1 2 t t h e p e r o v s k i t e NdxY1-xA103 o r t h e u n d i l u t e d p e n t a p h o s p h a t e NdP 05 1 4 ' N e v e r t h e l e s ~ ~ t h e t e r a w a t t l a s e r s [ 9 , 1 0 ] p r o v i d i n g n a n o s e c o n d 1 0 0 0 0
j o u l e p u l s e s f o r i n d u c i n g t h e r m o n u c l e a r f u s i o n i n d e u t e r i u m - t r i t i u m p e l l e t s a r e r a t h e r s p e c i a 1 , o p t i r n i z e d s i l i c a t e g l a s s 1 a s e r s . A ~ a l r e a d y s u g g e s t e d [ 3 ] b y t h e c r y s t a l l i n e f l u o r i d e s , t h e r e a r e g o o d r e a s o n s t o e x p e c t t h a t f l u o r i d e g l a s s e s may b e g o o d candidates.ActuallyIeight J- l e v e l s o f h o l m i u m (111) [ 11 -1 31 show p e r c e p t i b l e l u m i n e s c e n c e , a n d p e r f o r m c a s c a d e t r a n s i t i o n s ( l i k e g a s e o u s a t o m s ) i n ZBLA g l a s s o f t h e t y p e i n v e n t e d b y L u c a s [ l 4 ] w i t h m o l e c o m p o s i t i o n c l o s e t o 5 7 Z r F 4 : 34 BaF2 : 5 LnF3 : 4 A1F3 ( w h e r e t h e l a n t h a n i d e s Ln may i n c l u d e c o l o u r l e s s l a n t h a n u m ) . E r b i u m ( I I I ) i n ZBLA g l a s s I1 5 , 1 6 I s h o w s a l s o q u i t e e f f i c i e n t l u m i n e s c e n c e , a n d t h e p a r a m e t e r s o f e q . ( l ) a r e p r a c t i - c a l l y i d e n t i c a l w i t h t h o s e f o u n d f o r h o l m i u m ( I I I ) . T h e l o w e r l i m i t o f t h e e n e c y y g a p E s t i l l a l l o w i n g d e t e c t a b l e l u m i n e s c e n c e i s 1 9 0 0 t o 2 0 0 0 c m ( 0 . 2 4 eV) i n b o t h c a s e s , w h e r e a s m o s t 5 0 t h e r m t e r i a l s [ 2 ] h a v e t h i s l i m i t 2 t o 4 t i m e s h i g h e r . N o t o n l y DO a n d 'D b u t a l s o 5 D 2 a n d
50)
l u m i n e s c e s t r o n g l y o f e u r o p i u m ( I I 1 ) i n ZBLA g ! a s s [ l 7 1 . T h e c r i t l c a l e n e r g y g a p i s e v e n n a r r o w e r [ l 8 ] i n a g l a s s ( i n m o l e p e r c e n t )2 7 . 5 ThF4 : 2 6 . 8 7 5 ZnF2 : 9 BaF2 : 6 Z r F 4 : 5 NaF : 3 L i F : 0 . 1 2 5 LnF3 w h e r e t h r e e h o l m i u m ( I I 1 ) l e v e l a n d o n e e r b i u m ( I I 1 ) l e v e l h a v e e n e r g y g a p s m a r g i n a l l y b e l o w 1 8 0 0 c m
-7
a n d l i f e - t i m e s o f o r d e r 1 m i c r o s e c o n d . C o m p a r a b l e g l a s s e s c o n t a i n i n g a l a r g e n u m b e r o f m i x e d f l u o r i d e s a r e r e p o r t e d [ l 8 ] t o show s i m i l a r b e h a v i o u r .I t w o u l d b e c o n c e i v a b 3 e t h a t t h e f i r s t e x c i t e d q u a r t e t s t a t e 4 ~ 2 a n d l o w e s t d o u b l e t s t a t e E o f o c t a h e d r a l c h r o m i u m f I I I ) w o u l d h a v e q u i t e h i g h y i e l d s o f l u m i n e s c e n c e , a s known f r o m p h o s p h a t e g l a s s e s [ l 9 , 2 0 ] a n d v a r i o u s t r a n s l u c e n t ( a n d m e n l i m p i d ) g l a s s - c e r a m i c s [ 2 1 - 2 3 1 b u t t h e y i e l d i s v e r y l o w i n f l u o r i d e g l a s s e s [ 2 4 ] . T h e f i r s t e x c i t e d ( q u a r t e t )
s t a t e o f ( n o t n e c e s s a r i l y o c t a h e d r a l ) m a n g a n e s e ( I 1 ) h a s t h e same o r d e r o f ( m e a n ) l i f e - t i m e i n f l u o r i d e g l a s s e s a s 1 0 t o 1 5 m i l l i s e c o n d s i n a l a r g e n u m b e r o f p h o s p h a t e g l a s s e s [ 2 5 ] . T h i s l o n g - l i v e d q u a r t e t s t a t e o p e n s t h e p o s s i b i l i t y o f e n e r g y s t o r a g e f a c i l i t a t i n g l a s e r a c t i o n i n f l u o r i d e g l a s s e s containing,simultaneously,manganese(II) a n d t r i v a l e n t l a n t h a n i d e s . T h u s , Z B L A g l a s s c o n t a i n i n g o n e m o l e p e r c e n t e a c h o f MnF
s h o w s t h e l i f e - t i m e 0 . 3 4 m s o f t h e d i r e c t l u m i n e s c e n c e o f 2 e x t e n d e d t o a b o u t 1 . 5 m s b y e n e r g y t r a n s f e r f r o m m a n g a n e s e [ 2 4 ] .
$;d NdF3
s u S A 2 e f f e c t s w e r e a l s o o b s e r v e d [ 2 6 - 2 8 1 i n g l a s s e s o f t h e t y p e 36 PbF2 : 35 GaF3 : 24 MnF2 : 2 A1F3 : 3 YF3 : ( 4 - x ) LaF3 : x NdF3 w h e r e t h e l i f e - t i m e o f 4~ i n c r e a s e s f r o m 0 . 3 t o a l m o s t 1 m i l l i s e - c o n d b y e x c i t a t i o n i n t h e 3 / $ a n g a n e s e (11) a b s o r p t i o n b a n d s . S i m i l a r g l a s s e s ( p r e p a r e d b y J a c o b o n i a t U n i v e r s i t k d e M a i n e , L e Mans)
containing ZnF2 (rather than MnF ) and simultaneously NdF and4YbF allowed a detall d comparison[297 of the energy transfer 2rom F 3 of neodymium to 'F of ytterbium(II1) .Such energy transfer was 3/2 studied earlier[30y'$n a less quantitative way between several J- levels of erbium(II1) and (in both directions) the lowest quartet of simultaneously present manganese(I1) in a lead gallium fluoride glass containing also some A1(P03!3.Recently,there has been some interest in fluoride glasses containing uranyl ions[31] having the longest observed life-time 0.63 ms in a glass,to be compared[32] with 1 to 2 milliseconds in some crystalline uranyl compounds.
When prospecting for potential laser materialsfit is very helpful that small-scale e ~ p e r i m e n t a t i o n [ l , 2 ~ 2 8 ~ 3 3 ] mainly involving the time-evolution of spectroscopic properties can serve as a reliable guide-line for predicting laser performance.At the moment,the major technological interest in fluoride glasses is centered on optical fibers for infrared long-distance transmission of signals[34].
However,as already widely elaborated,they have outstanding luminescent properties,when containing 1anthanides.Besid.e~ the low vibrational frequencies expressed in eq.(l),the electron transfer bands of fluorides[35] have higher energy than of any other kind of ligands
(when connected to a given oxidizing transition-group atom with an empty or partly filled 3d14d,5d,4f or 5f shell) and it is known[361 that the de-excitation of excited J-levels of europium(II1) in mixed oxides is connected with the potential surfaces of the electron transfer states.The oxidizing character of a given trivalent or quadrivalent lanthanide as a function of the number of 4f electrons is rationalized [I ,37,38] by the spin-pairing energy treatment .It is also specific for fluoride glasses[28,39] that they do not contain network-formers in the same sense as silicate and phosphate glasses, and that the local symmetry and coordination number N of incorporated luminescent ions can be quite versatile,and in the case of lanthanides probably assume all N values from 7 to 12 without pronounced energetic preference.
Acknowledgements.
I am grateful to Professor Renata Reisfeld for valuable discussions.
This collaboration were supported by 2.820-0.85 (and previous grants) from the Swiss National Science Foundation.
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