42 JOURNAL OF THE ELECTROCHEMICAL SOCIETY J a n u a r y 1964

Conclusions
E l e c t r o d e p o s i t e d films show a p a r t i a l r o t a t i o n a l
s w i t c h i n g b e h a v i o r s i m i l a r to t h a t r e p o r t e d for
v a c u u m deposited films as e v i d e n c e d b y (i) a c i r c u -
l a r flux path, a n d (it) r o t a t i o n a l thresholds. T h e
H c / H k ratio d e t e r m i n e s t h e m i n i m u m a n g l e b e -
t w e e n t h e easy axis a n d the a p p l i e d field for c o h e r -
e n t r o t a t i o n a l s w i t c h i n g . I n c r e a s i n g d i s p e r s i o n at a
fixed H c / H k ratio r e d u c e s t h e w a l l m o t i o n t h r e s -
hold. The w a l l m o t i o n a n d r o t a t i o n a l t h r e s h o l d

!' , , , ,
0
400
6 0 8 0 IOOO 1200 1400
THICKNESS, A~
Fig. 4. Separation between rotational and wall motion thresholds
at a fixed bias field.
The separation b et w een the wall motion and ro-
t a t i o n a l t h r e s h o l d s ( A h n ) at a fixed d - c bias field
a p p e a r s to be p r i m a r i l y d e p e n d e n t on the t h i c k n e s s
of the film. T h e r e does n o t a p p e a r to be a n y d i r e c t
c o r r e l a t i o n of w a l l m o t i o n a n d r o t a t i o n a l t h r e s h o l d
s e p a r a t i o n w i t h m a x i m u m d i s p e r s i o n or H c / H k
ratio. A plot of w a l l m o t i o n a n d r o t a t i o n t h r e s h o l d
s e p a r a t i o n (Ahl~) vs. t h i c k n e s s is s h o w n i n Fig. 4
at d - c bias fields of 0.4 H a n d at 0.7 H
These r e s u l t s show t h a t t h e m a x i m u m s e p a r a t i o n
occurs as the t h i c k n e s s is decreased o v e r the r a n g e
of t h i c k n e s s m e a s u r e d ( 5 0 0 - 1 4 0 0 A ) . T h e effect of
t h i c k n e s s on the s e p a r a t i o n ( A h n ) m a y be associ-
ated w i t h the t y p e of w a l l f o r m a t i o n . T h e w a l l m o -
tion threshold may decrease with increasing thick-
ness d u e to a c h a n g e f r o m Neel to C r o s s - T i e to Bloch
w a l l f o r m a t i o n . T h u s a Bloch w a l l w o u l d h a v e a
l o w e r w a l l m o t i o n t h r e s h o l d t h a n a Neel wall.
s e p a r a t i o n is p r i m a r i l y d e p e n d e n t on t h i c k n e s s .
Magnetization path and threshold measurements
c l e a r l y show t h a t two m e c h a n i s m s of s w i t c h i n g oc-
c u r d u r i n g flux r e v e r s a l , a r o t a t i o n a l s w i t c h fol-
l o w e d b y a w a l l m o t i o n s w i t c h as the m a g n e t i z a t i o n
moves through the hard direction.
Acknowledgment
T h e a u t h o r s w o u l d like to e x p r e s s a p p r e c i a t i o n to
T h o m a s S. C r o w t h e r for h e l p f u l c o m m e n t s o n this
manuscript.
Manuscript received May 13, 1963. This paper was
presented at the P i t t s b u r g h Meeting, April 15-18, 1963.
A n y discussion of this paper will appear in a Discus-
sion Section to be published in the December 1964
JOURNAL.
REFERENCES
1. I. W. Wolf, This Journal, 108, 959 (1961).
2. R. D. Fisher and H. E. Haber, Letters J. Appl. Phys.,
Vo]. 2, No. 1, p. 11 (1963).
3. E. C. Stoner and E. P. Wohlfarth, Phil. Trans. Roy.
Sac. (London), A240, 599 (1948).
4. T. S. Crowther, Lincoln Lab Report 51-2, F e b r u a r y
1959.
5. S. Methfessel, S. Middelhoek, and H. Thomas, J.
Appl. Phys., 32, 1959 (1961).
6. S. Middelhoek, I.B.M. Journal, p. 394 (October 1962).

Chemical Deposition of Thin Films of Lead Selenide

Ralph A. Zingaro and Dean O. Skovlin
Department of Chemistry, Agricultural and Mechanical College o~ Texas, College Station, Texas

ABSTRACT
A method has been developed which yields chemically deposited thin films
of lead selenide on a glass surface. These are u n i f o r m in appearance and elec-
trical resistance [1-4 meg/(0.635 cm)2]. The coating solution is made up of a
lead citrate complex and dimethylselenourea with sodium sulfite p r e s e n t as an
antioxidant. All of the p a r a m e t e r s involved in the coating process were studied,
i n c l u d i n g the p r e t r e a t m e n t of the glass surface, and the o p t i m u m conditions for
the coating reaction are described.

T h e m e t h o d of p r e p a r i n g t h i n films of lead c h a l c o - v a l v e d c h a n g e s i n the c o n c e n t r a t i o n s of t h e lead

genides by homogeneous precipitation from solution
has r e c e i v e d r e l a t i v e l y little a t t e n t i o n . T h e m e t h o d
is of c o n s i d e r a b l e i n t e r e s t b e c a u s e it r e a d i l y l e n d s
itself to l a r g e - s c a l e p r o d u c t i o n t e c h n i q u e s .
T h e c h e m i c a l d e p o s i t i o n of l e a d sulfide films w a s
d e s c r i b e d b y H a u s e r (1) i n 1910. T h i s m e t h o d i n -
volves the r e a c t i o n of d i l u t e s o l u t i o n s of t h i o u r e a
w i t h l e a d acetate. A l m o s t all s u b s e q u e n t i n v e s t i g a -
tions d e a l i n g w i t h t h e c h e m i c a l d e p o s i t i o n of lead
sulfide e s s e n t i a l l y h a v e e m p l o y e d modifications of
Hauser's method. The principle variations have in-
a c e t a t e a n d t h i o u r e a s o l u t i o n s used, t h e t e m p e r a t u r e
of deposition, a n d t h e use of s u r f a c e s e e d i n g n u c l e i as
a m e a n s of i m p r o v i n g t h e p r o p e r t i e s of t h e films. A n
e x c e p t i o n to t h e lead a c e t a t e - t h i o u r e a r e a c t i o n is t h e
m e t h o d d e s c r i b e d b y W i l m a n (2). I n this case h y d r o -
g e n sulfide is passed o v e r a n acidic s o l u t i o n of l e a d
a c e t a t e a n d a floating film of lead sulfide is f o r m e d .
P i c k (3) has discussed t h e factors w h i c h i n f l u e n c e
film f o r m a t i o n i n h o m o g e n e o u s p r e c i p i t a t i o n r e a c -
tions. T h e s e i n c l u d e the r a t e of diffusion of colloidal
p a r t i c l e s to t h e glass s u r f a c e a n d the i n f l u e n c e of
Vol. 111, No. 1 DEPOSITION OF FILMS
crystallization nuclei which can be formed by the
a d d i t i o n of m e t a l ions w h o s e sulfides a r e e x t r e m e l y
i n s o l u b l e such as s i l v e r , m e r c u r y , p l a t i n u m , a n d
gold. T h e m e c h a n i s m of p r e c i p i t a t i o n of l e a d sulfide
o u t of a l k a l i n e l e a d - t h i o u r e a s o l u t i o n s in t e r m s of a
thiourea-lead hydroxide complex has been discussed
by Kicinski (4).
T h e c h e m i c a l d e p o s i t i o n of t h i n films of l e a d
selenide has been only scantily investigated. This has
b e e n due, in l a r g e p a r t , to t h e i n s t a b i l i t y of t h e
organic selenium bearing compounds which have
b e e n u s e d as p r e c i p i t a n t s .
W i l m a n (2) h a s d e s c r i b e d t h e f o r m a t i o n of a t h i n
m i r r o r of l e a d s e l e n i d e on t h e s u r f a c e of l e a d a c e t a t e
s o l u t i o n s acidified w i t h acetic a c i d o v e r w h i c h h y -
d r o g e n s e l e n i d e w a s p a s s e d . T h e s u r f a c e m i r r o r of
l e a d s e l e n i d e w a s c a r e f u l l y f l o a t e d on t h e s u r f a c e of
a n i c k e l gauze, w a s h e d , a n d d r i e d in vacuo.
A m e t h o d d e s c r i b e d b y M i l n e r a n d W a t t s (5) i n -
v o l v e s t h e r e a c t i o n of l e a d a c e t a t e w i t h s e l e n o u r e a
in a q u e o u s solution. P r i o r to c a r r y i n g o u t t h i s r e a c -
tion, a v e r y t h i n film of l e a d sulfide is d e p o s i t e d on
t h e s u r f a c e to b e c o a t e d . This fine d e p o s i t f u r n i s h e s
t h e n u c l e i w h i c h act as a s e e d i n g l a y e r f o r t h e
g r o w t h of m i c r o c r y s t a l l i n e l e a d selenide. T h e l e a d
sulfide l a y e r is p r e p a r e d b y i m m e r s i o n , f o r a s h o r t
t i m e , of t h e s u r f a c e to b e c o a t e d in a b a t h of l e a d
a c e t a t e a n d t h i o u r e a w h i c h is m a d e i n c r e a s i n g l y
a l k a l i n e . A f t e r r e m o v a l of t h i s solution, l e a d s e l e n i d e
is t h e n d e p o s i t e d on t h e s e e d e d s u r f a c e b y t h e r e a c -
t i o n of a s o l u t i o n of s e l e n o u r e a a n d l e a d a c e t a t e . T h e
r e a c t i o n is v e r y s l o w a n d a b o u t a n h o u r is r e q u i r e d
for t h e d e p o s i t i o n of a sufficiently t h i c k l a y e r of l e a d
s e l e n i d e . T h e s e i n v e s t i g a t o r s g i v e no i n f o r m a t i o n
r e g a r d i n g t h e c o n d i t i o n s of t h e r e a c t i o n , t h e s t a b i l i t y
of t h e s e l e n o u r e a solution, or t h e c o n c e n t r a t i o n of
reagents used.
The present work describes a method which uti-
lizes d i m e t h y l s e l e n o u r e a ( D M S ) as t h e p r e c i p i t a n t
a n d u t i l i z e s c i t r a t e ion to c o n t r o l t h e l e a d ion c o n -
c e n t r a t i o n . D e t a i l s on v a r i o u s p h a s e s of t h e h o m o -
g e n e o u s p r e c i p i t a t i o n of l e a d s e l e n i d e a r e d e s c r i b e d ,
a n d l e a d s e l e n i d e m i r r o r s of r e p r o d u c i b l e p h y s i c a l
a n d e l e c t r i c a l p r o p e r t i e s c a n b e f o r m e d easily.
Experimental
Selection of reagents.--Selenourea is difficult to
p r e p a r e a n d q u i t e u n s t a b l e . T h e r e f o r e , its d e r i v a t i v e ,
N , N - d i m e t h y I s e l e n o u r e a w a s used. I t s p r e p a r a t i o n is
e a s i l y a c c o m p l i s h e d ( 6 ) . On e x p o s u r e to a i r a n d
light DMS deposits red, colloidal selenium. Storage
in a d r y n i t r o g e n a t m o s p h e r e in a l i g h t - t i g h t c o n -
t a i n e r i n h i b i t s such d e c o m p o s i t i o n i n d e f i n i t e l y .
Stabilization of aqueous DMS solutions.--In o r d e r
to i n h i b i t t h e d e c o m p o s i t i o n of D M S f r o m its a q u e -
ous solutions, a v a r i e t y of a n t i o x i d a n t s w e r e i n v e s t i -
g a t e d . T h e s e i n c l u d e d a s c o r b i c acid, s o d i u m sulfite,
sodium thiosulfate, hydroquinone, formaldehyde,
a n d d i s p l a c e m e n t of d i s s o l v e d o x y g e n b y s a t u r a t i o n
of t h e s o l u t i o n w i t h n i t r o g e n gas. F i r s t e v i d e n c e of
s e l e n i u m d e p o s i t i o n f r o m 0.11V[ a q u e o u s s o l u t i o n s of
D M S in t h e a b s e n c e of a n y i n h i b i t o r s w a s o b s e r v e d
a f t e r 3 min. F o r m a l d e h y d e a c t u a l l y a p p e a r s to c a t a -
l y z e t h e o x i d a t i o n ; s e l e n i u m d e c o m p o s i t i o n in such
s o l u t i o n w a s o b s e r v e d to o c c u r less t h a n 30 sec a f t e r
OF LEAD SELENIDE 43
m i x i n g . S o m e of t h e o t h e r a n t i o x i d a n t s e x t e n d e d t h e
i n h i b i t i o n p e r i o d b y 2 to 17 min. M a x i m u m i n h i b i -
tion was observed with ascorbic acid and sodium
sulfite; t h e first e v i d e n c e of s e l e n i u m d e c o m p o s i t i o n
u s i n g t h e s e r e a g e n t s at O.IM c o n c e n t r a t i o n w a s in
e x c e s s of 72 hr. S o d i u m sulfite w a s t h e a n t i o x i d a n t
s e l e c t e d b e c a u s e i n s u b s e q u e n t e v a l u a t i o n it w a s
f o u n d to y i e l d m i r r o r s of a m u c h m o r e h o m o g e n e o u s
quality.
Complexing of the lead ion.--Because of t h e r e a d y
p r e c i p i t a t i o n of l e a d h y d r o x i d e , e s p e c i a l l y a t h i g h e r
p H ' s , s t u d i e s of t h e r e a c t i o n in a l k a l i n e s o l u t i o n
c o u l d b e c a r r i e d o u t o n l y in a m e d i u m in w h i c h t h e
l e a d i o n c o n c e n t r a t i o n w a s r e d u c e d to a l e v e l so l o w
t h a t t h e s o l u b i l i t y p r o d u c t for l e a d h y d r o x i d e w a s
n o t e x c e e d e d . A s a r e s u l t , v a r i o u s c o m p l e x i n g ions,
s u c h as o x a l a t e , t a r t r a t e , a n d c i t r a t e , w e r e i n v e s t i -
g a t e d as c o m p l e x i n g a g e n t s . Of these, o n l y c i t r a t e
w a s f o u n d to b e effective; t h e o t h e r t w o f o r m e d p r e -
c i p i t a t e s i n s o l u b l e in a n e x c e s s of t h e ions.
T h e use of e x c e s s c i t r a t e r e d u c e s t h e c o n c e n t r a t i o n
of l e a d ion a n d p e r m i t s a n i n c r e a s e in p H w i t h still
f u r t h e r r e d u c t i o n in t h e f r e e l e a d ion c o n c e n t r a t i o n .
This w i l l b e d i s c u s s e d s u b s e q u e n t l y .
Effect of pH on mirror formation.--Lead-citrate
s o l u t i o n s w e r e p r e p a r e d f r o m 5.0 m l l e a d n i t r a t e
(0.1M) a n d 2.5 m l s o d i u m c i t r a t e ( 0 . 8 M ) . A m m o -
n i u m h y d r o x i d e (7.5M) w a s a d d e d s t e p w i s e , a n d t h e
p H of t h e s o l u t i o n w a s m e a s u r e d at e a c h s t e p w i t h a
model H-2 Beckman pH meter.
To d e t e r m i n e t h e o p t i m u m p H for t h e d e p o s i t i o n
of l e a d s e l e n i d e m i r r o r s , v a r i o u s l e a d - c i t r a t e s o l u -
tions c o n t a i n i n g v a r y i n g a m o u n t s of a m m o n i u m h y -
d r o x i d e w e r e p r e p a r e d as d e s c r i b e d a n d t e s t e d . I n
e a c h case, 5.0 m l of D M S ( 0 . 1 M ) , c o n t a i n i n g s o d i u m
sulfite (0.01M) as t h e a n t i o x i d a n t , w a s a d d e d to t h e
a m m o n i a c a l l e a d - c i t r a t e s o l u t i o n a n d t h e s p e e d of
t h e r e a c t i o n a n d n a t u r e of t h e l e a d s e l e n i d e m i r r o r
formed were noted.
T h e b e s t films w e r e p r o d u c e d f r o m s o l u t i o n s h a v -
i n g a p H of 9.8. S m o o t h , e v e n m i r r o r s w e r e d e p o s i t e d
a f t e r 30 m i n of r e a c t i o n . T h e r e a c t i o n in t h e s o l u t i o n
h a v i n g a p H of 9.5 w a s too slow; a thin, u n e v e n film
w a s p r o d u c e d a f t e r 1 h r of r e a c t i o n . G r o s s p r e c i p i t a -
t i o n o c c u r r e d in t h e s o l u t i o n of p H 10.1, w i t h t h e
f o r m a t i o n of a thin, u n e v e n m i r r o r . A p H of 9.8
w a s s e l e c t e d a n d u s e d in a l l f u r t h e r e x p e r i m e n t s .
Effect of aging on the stability of DMS-sul~te
soIutioc~s.--It w a s o b s e r v e d , w h e n u s i n g s o d i u m s u l -
rite as t h e a n t i o x i d a n t , t h a t t h e d e p o s i t i o n r e a c t i o n
did not always proceed at the same rate. Not only
d i d t h e p r e - m i r r o r i n g t i m e v a r y b u t also t h e a m o u n t
of m i r r o r d e p o s i t i o n . This effect w a s f o u n d to b e d u e
to t h e t i m e e l a p s e d b e t w e e n t h e p r e p a r a t i o n a n d
use of t h e D M S - s u l f i t e solutions. F r e s h l y p r e p a r e d
solutions gave a very slow reaction, whereas older
solutions reacted more rapidly.
A s t u d y of t h e effect of a g i n g on t h e s p e e d of t h e
reaction was made by following the light trans-
m i s s i o n of t h e l e a d s e l e n i d e s u s p e n s i o n u s i n g a
C e n c o - S h e a r d - S a n f o r d P h o t e l o m e t e r , T y p e B2. T h e
deposition reaction was studied using various sam-
ples of t h e D M S - s u l f i t e s o l u t i o n s of t h e s a m e c o n -
c e n t r a t i o n , b u t f o r w h i c h d i f f e r e n t i n t e r v a l s of t i m e
h a v e e l a p s e d b e t w e e n t h e t i m e of p r e p a r a t i o n a n d t h e
44 JOURNAL OF THE ELECTROCHEMICAL SOCIETY January 1964

F D C B A
90
I
8r 80
_g ~c 70

:~ 6C ~ffl 6o
in
z
~ 5c
~ 4c

2C

I
o ' ' ~ ' 7' '~ ' ,'o ,'.... ', ,', ,~I o io 20 II 2'o 4'o I'
2
~; ,~o '
$
~'o ,~o I
4
REACTION TIME (MIN.)
REACTION TIME (MINUTES)

Fig. 1 Effect of aging of the DMS-sulfite solution on the rate Fig. 3. Reproducibility of homogeneous lead selenide pre-
of precipitation of lead selenide. Prereaction aging time: A, 6 rain; cipitation. Ideally, the five curves would be entirely superimposed.
B, 1 hr; C, 2 hr; D, 4 hr; E, 6 hr; F, 21 hr. Solution aging time, 1 hr.

r e a c t i o n w i t h l e a d - c i t r a t e solution. T h e t r a n s m i s s i o n the p r e p a r a t i o n of lead s e l e n i d e m i r r o r s . O n e of t h e

of w h i t e l i g h t b y t h e s o l u t i o n w a s o b s e r v e d as a p a r a m e t e r s s t u d i e d w a s t h e r e p r o d u c i b i l i t y of t h e
f u n c t i o n of t o t a l r e a c t i o n time. T h e p h o t e l o m e t e r p r e - m i r r o r i n g reaction. This w a s e v a l u a t e d b y
was o p e n e d to its m a x i m u m slit w i d t h a n d no filter s t u d y i n g p h o t o m e t r i c a l l y t h e r e a c t i o n t i m e for a
was used. T h e t i m e p l o t t e d as the abscissa in Fig. 1 n u m b e r of solutions h a v i n g w h a t was c o n s i d e r e d to
is t h a t r e q u i r e d for t h e n e e d l e to m o v e f r o m the p o s i - be o p t i m u m composition. T h e s o l u t i o n s w e r e m a d e
t i o n of e x t r e m e deflection to t h e p e r cent t r a n s m i s - up as follows: lead s o l u t i o n : 2.5 m l s o d i u m c i t r a t e
sion noted. It c a n b e seen t h a t the effect of a g i n g of (0.4M), 5.0 m l l e a d n i t r a t e (0.1M), 0.4 m l a m m o -
t h e D M S - s u l f i t e s o l u t i o n s o n t h e r a t e of f o r m a t i o n of n i u m h y d r o x i d e (7.5M) ; D M S s o l u t i o n : 5.0 m l DMS
l e a d s e l e n i d e is critical. R e a d i n g s b e l o w 40% t r a n s - (0.1M) i n s o d i u m sulflte (0.01M, 0.0755 g ) ; a g i n g
m i s s i o n a r e of l i m i t e d v a l u e b e c a u s e of t h e f o r m a t i o n
time, 5.0 m i n .
of a t h i n reflecting film of lead s e l e n i d e on t h e r e - Solutions were prepared in a constant temperature
a c t i o n t u b e surface. bath (25~ a n d r e m a i n e d i n the b a t h u n t i l p l a c e d
I n Fig. 2 the r e a c t i o n t i m e of t h e h o m o g e n e o u s i n t h e p h o t e l o m e t e r . A r e d filter w a s used, a n d t h e
p r e c i p i t a t i o n is p l o t t e d vs. t h e a g i n g t i m e of t h e
p h o t e l o m e t e r w a s a d j u s t e d to 100% t r a n s m i s s i o n
D M S - s u l f i t e solution. I n this case, the t i m e r e q u i r e d
with the lead-citrate solution after which the DMS-
for t h e s o l u t i o n to r e a c h 90% t r a n s m i s s i o n w a s sulfite w a s a d d e d a n d t h e stop w a t c h e n e r g i z e d . T h e
chosen as a s t a n d a r d so t h a t m i r r o r f o r m a t i o n w o u l d
d a t a as p l o t t e d i n Fig. 3 s h o w t h a t a h i g h l y r e p r o -
n o t i n t e r f e r e . This plot shows that, for D M S - s u l f i t e
d u c i b l e p r e - m i r r o r i n g r e a c t i o n c a n be achieved. I n
s o l u t i o n s m o r e t h a n 10 h r old, a g i n g is o n l y of sec-
v i e w of t h e fact t h a t all s a m p l e s w e r e p r o b a b l y n o t
ondary importance.
heated u n i f o r m l y and the m a n y other variables that
Conditions for reproducibility of P b S e deposition.
could be i n t r o d u c e d , t h e r e p r o d u c i b i l i t y a c h i e v e d is
- - O n e of t h e basic o b j e c t i v e s of this i n v e s t i g a t i o n
excellent.
w a s to e s t a b l i s h a r e p r o d u c i b l e set of c o n d i t i o n s for
S t u d y of film resistance as a function of D M S -
sulfite aging.--Solutions at o p t i m u m c o a t i n g c o m -
12
p o s i t i o n (see p r e v i o u s s e c t i o n ) w e r e b r o u g h t to c o n -
stant temperature (25~ a glass slide ( t r e a t e d as
+~ _mlo d e s c r i b e d s u b s e q u e n t l y ) was p l a c e d i n the lead s o l u -
LU~
tion, a n d the DMSosulfite s o l u t i o n was added. T h e
~Z
Z~ test t u b e was g e n t l y s w i r l e d to i n s u r e c o m p l e t e
mN m i x i n g of the s o l u t i o n a n d t h e n p l a c e d i n t h e 25 ~
-JO
o
b a t h . T h e r e a c t i o n w a s p e r m i t t e d to p r o c e e d for 30.0
ul U m i n . A f t e r this t i m e t h e s o l u t i o n w a s r e m o v e d f r o m
~_<
t h e c o n s t a n t t e m p e r a t u r e b a t h , p o u r e d out, a n d t h e
test t u b e c o n t a i n i n g t h e glass slide r i n s e d w i t h dis-
~0 o t i l l e d w a t e r . T h e slide was t h e n r i n s e d s e p a r a t e l y
a n d d r i e d i n 110 ~ o v e n for 10 m i n . T h e r e s i s t a n c e s
w e r e m e a s u r e d a f t e r t h e p r e p a r a t i o n of e l e c t r o d e
z~ surfaces as d e s c r i b e d i n t h e n e x t section.
~_J
Preparation of electrodes.--While b e i n g coated
I I I I w i t h l e a d selenide, t h e slide r e s t e d i n t h e c o a t i n g
2I / / l i/ 112 14 16 118 20 22

AGING TIME N,N-DIMETHYLSELENOUREA-SULFITE (HOURS)

Fig. 2. Effect of aging of the DMS-sulfite solution on the rate
of lead selenide precipitation; the ordinate is the time required
for a lead citrate-DMS, sulfite mixture to reduce a beam of light
of equal intensity to 90 per cent of its initial intensity.
b a t h at a n a n g l e of a p p r o x i m a t e l y 60 ~ ( c y l i n d r i c a l
f l a t - b o t t o m e d vessels of p r o p e r d i a m e t e r s h o u l d be
u s e d as c o a t i n g c o n t a i n e r s so t h a t t h e slide c a n rest
at a p p r o x i m a t e l y this a n g l e ) . Thus, the s u r f a c e of
the slide f a c i n g t h e b o t t o m of t h e t u b e could be
Vol. 111, No. 1 DEPOSITION OF
12
1
I0
2=
t~J
~6
2
#
N , N - D I M E T H Y L S E L E N O U R E A - S U L F I T E AGING, HOURS
Fig. 4. Resistivity of chemically deposited lead selenide films
on glass as a function of the aging time of the DMS-sulfite
solution.
c o a t e d b y a d s o r p t i o n of l e a d s e l e n i d e p a r t i c l e s w h i l e
t h e u p p e r side c o u l d b e c o a t e d b y s e d i m e n t a t i o n as
well. T h e film on t h e u n d e r side of t h e s l i d e w a s
u s e d f o r r e s i s t a n c e m e a s u r e m e n t s . T h i s side w a s
e a s i l y d i s t i n g u i s h e d f o r it p o s s e s s e d a v e r y b r i g h t ,
even, r e f l e c t i n g s u r f a c e w h i l e t h e u p p e r s i d e w a s
d u l l a n d s o o t y in a p p e a r a n c e .
T h e l e a d s e l e n i d e on t h e b a c k s i d e of t h e s l i d e w a s
removed by rubbing with a cotton swab moistened
in 10% n i t r i c acid, a n d t h e film a l o n g t h e e d g e s w a s
r e m o v e d b y r u b b i n g w i t h e m e r y cloth. A q u a d a g
e l e c t r o d e s w e r e t h e n p a i n t e d at t h e e d g e s of t h e l e a d
selenide surface while masking the center portion
w i t h s m o o t h p a p e r s t r i p e x a c t l y 0.635 c m in w i d t h .
T h e r e s i s t a n c e of films p r e p a r e d in t h e m a n n e r d e -
s c r i b e d in t h e s e c t i o n i m m e d i a t e l y p r e c e d i n g , b u t in
w h i c h D M S - s u l f i t e s o l u t i o n s h a d a g e d f r o m 2-16 h r
is s h o w n in Fig. 4. T h e s h a p e of t h i s c u r v e c l o s e l y
r e s e m b l e s t h a t of Fig. 2. A g a i n it is s h o w n t h a t
a f t e r 10 h r t h e a g e of t h e D M S - s u l f i t e is no l o n g e r a
critical factor.
Pretreatment of the glass surface.--Pick (3) o b -
s e r v e d t h a t t h e c o n d i t i o n of t h e glass s u r f a c e p r o -
f o u n d l y affected t h e q u a l i t y of l e a d sulfide m i r r o r
deposition. Seeding nuclei play a very important
r o l e in d e t e r m i n i n g b o t h t h e t y p e a n d a m o u n t of
mirror deposited.
A s a m e a n s of o b t a i n i n g a m o r e u n i f o r m a n d r e -
p r o d u c i b l e d e p o s i t i o n , t h r e e m e t h o d s of i n t r o d u c i n g
s e e d i n g n u c l e i on t h e g l a s s s u r f a c e w e r e u s e d : b a t h -
ing t h e s l i d e in a c o l l o i d a l solution, i n t r o d u c t i o n of a
c a t i o n w h i c h f o r m s a n i n s o l u b l e s e l e n i d e in t h e r e -
a c t i o n m e d i u m , a n d p r e e o a t i n g t h e glass s u r f a c e w i t h
a v e r y l i g h t film of l e a d s e l e n i d e .
P r i o r to m i r r o r i n g , t h e s l i d e s w e r e p l a c e d in c o l -
l o i d a l s o l u t i o n s of s i l v e r i o d i d e ( 7 ) , g o l d ( 8 ) , a n d
l e a d sulfide (9) f o r 10 rain. T h e s l i d e s w e r e t h e n
t r a n s f e r r e d d i r e c t l y to t h e l e a d - c i t r a t e solution. M i r -
r o r s w e r e t h e n o b t a i n e d in e x a c t l y t h e s a m e m a n n e r
as d e s c r i b e d u s i n g D M S - s u l f i t e s o u t i o n s t h a t w e r e
a g e d for 1.0 h r in a l l cases. T h i s t y p e of p r e t r e a t -
m e n t in s i l v e r i o d i d e a n d l e a d sulfide sols a d v e r s e l y
a f f e c t e d t h e q u a l i t y of t h e m i r r o r deposit. I n a l l cases
FILMS OF LEAD SELENIDE 45
very thin and uneven mirrors were formed. Pre-
i m m e r s i o n in t h e c o l l o i d a l g o l d s u s p e n s i o n p r o d u c e d
a n e x t r e m e l y u n i f o r m film, b u t it w a s v e r y thin.
Lead-citrate solutions were prepared that were
1 0 - 4 M in s i l v e r o r c o p p e r ( I I ) ion c o n c e n t r a t i o n .
M i r r o r s w e r e t h e n p r e p a r e d in e x a c t l y t h e s a m e w a y
as a b o v e , u s i n g D M S - s u l f i t e s o l u t i o n s a g e d f o r 1.0 hr.
A f t e r 30.0 rain, t h e m i r r o r p r e p a r e d in p r e s e n c e of
t h e s i l v e r ion h a d p e e l e d c o m p l e t e l y . A f t e r 66.0 rain,
t h e m i r r o r p r e p a r e d in t h e p r e s e n c e of C u ( I I ) ion
was very thin, uneven, and spotty.
M i r r o r s f o r m e d in t h e p r e s e n c e of 10 - 5 a n d 1 0 - 6 M
s i l v e r ion d i d n o t p e e l a f t e r a 3 0 . 0 - m i n d e p o s i t i o n
a n d w e r e v e r y even. R e s i s t a n c e s of t h e films p r e -
p a r e d f r o m l e a d s o l u t i o n s c o n t a i n i n g 10 - 5 a n d 10-6M
s i l v e r ion h a d r e s i s t a n c e s of 11 a n d 21 meg'ohms,
r e s p e c t i v e l y . A film f o r m e d u n d e r l i k e c o n d i t i o n s
b u t w i t h s i l v e r ion a b s e n t h a d a r e s i s t a n c e o f 37
megohms.
G l a s s slides w e r e p l a c e d in t h e 7.9 m l s t a n d a r d
l e a d c i t r a t e s o l u t i o n a n d 5.0 m l D M S - s u l f i t e ( a g i n g
t i m e , 5.0 r a i n ) w a s t h e n a d d e d . T h e r e a c t i o n w a s a l -
l o w e d to p r o c e e d at 25 ~ for 7.0 min. T h e r e a c t i o n w a s
s t o p p e d b y p o u r i n g off t h e s o l u t i o n a n d r i n s i n g t h e
test tube containing the slide with distilled water.
T h e slide, a f t e r r i n s i n g , w a s c o a t e d w i t h a v e r y l i g h t
film of l e a d s e l e n i d e . T h e l i g h t l y c o a t e d s l i d e w a s
t h e n p l a c e d in a n o t h e r s t a n d a r d l e a d c i t r a t e s o l u t i o n
a n d 5.0 m l of a s e c o n d D M S - s u l f i t e s o l u t i o n ( a g i n g
t i m e , 16.0 h r ) w a s t h e n a d d e d . A f t e r 30.0 m i n at 25 ~
the reaction was stopped. The slide was rinsed and
d r i e d a t 110 ~ for 10 m i n . T h e s l i d e s w e r e p r e p a r e d
f o r r e s i s t a n c e m e a s u r e m e n t s as d e s c r i b e d p r e v i o u s l y .
R e s i s t a n c e s o b t a i n e d on s i x t e e n slides p r e p a r e d in
t h i s m a n n e r w e r e as f o l l o w s : 3.0, 4.0, 1.8", 0.7*, 1.1,
2.0, 2.2, 1.9, 2.8, 3.2, 2.0", 1.4", 2.2, 4.0, 3.8, a n d 3.7
m e g / ( 0 . 6 3 5 c m ) 2, w h e r e t h e figures m a r k e d w i t h a n
a s t e r i s k i n d i c a t e t h a t t h e l e a d s e l e n i d e film h a d
p e e l e d . This m e t h o d p r o d u c e d slides w i t h c o n s i d e r -
a b l e less v a r i a t i o n in r e s i s t a n c e a n d of g r e a t e r u n i -
f o r m i t y a n d a d h e s i o n t h a n w i t h a n y o t h e r set of
conditions investigated.
It was noted, when precoated slides were used,
t h a t l e a d s e l e n i d e p a r t i c l e s s t a r t e d to g r o w at t h e
u n d e r s u r f a c e of t h e s l i d e a l m o s t i m m e d i a t e l y a f t e r
t h e c o a t i n g s o l u t i o n s w e r e m i x e d . T h e a t t r a c t i o n of
colloidal lead selenide for the treated surface was
such that the coating on the slide appeared opaque
b e f o r e a n y m i r r o r i n g t o o k p l a c e on t h e u n t r e a t e d
w a l l s of t h e c o n t a i n e r .
Discussion
T h e r a t e of h o m o g e n e o u s p r e c i p i t a t i o n of l e a d
s e l e n i d e in t h e s y s t e m j u s t d e s c r i b e d w i l l b e d e t e r -
mined largely by the lead ion concentration. The
l e a d i o n c o n c e n t r a t i o n will, at t h e p H e m p l o y e d in
the reaction, be governed by the following equilib-
r i u m (10)
Pb+2 + Ci-3 + OH- ~ PbCi*-2 + H20 [1]
w h e r e t h e Ci* is t h e c o m p l e t e l y i o n i z e d t e t r a v a l e n t
c i t r a t e ion. T h e u s e of s o d i u m p l u m b i t e , w h o s e f o r -
m a t i o n r e q u i r e s a v e r y l a r g e e x c e s s of h y d r o x y l ion,
Was f o u n d to b e q u i t e u n d e s i r a b l e since it l e a d s to
a gross, b u l k , p r e c i p i t a t i o n of l e a d s e l e n i d e . T h i s
46 JOURNAL OF THE ELECTROCHEMICAL
m a y be d u e also to t h e i n s t a b i l i t y of DMS i n h i g h l y
a l k a l i n e solutions.
The most p r o b a b l e m e c h a n i s m b y w h i c h DMS o x i -
dizes is t h e f o l l o w i n g :
1. E q u i l i b r i u m w i t h h y d r o g e n s e l e n i d e
(CH:3) 2 N
\ c e n t r a t i o n s . T h e lead ion c o n c e n t r a t i o n w o u l d b e r e -
C : Se ~--~H2Se + ( C H 3 ) 2 N - - C = N [2]
/ f o r m e d i n solution. T h e f o r m a t i o n of a lead sulfite
H2N
2. I o n i z a t i o n of H2Se
H2Se ~ H + ~- H S e - [3]
H S e - ~-~ H + -~ Se = [4]
3. O x i d a t i o n of s e l e n i d e ion
Se = -) Se ~- 2 e - [5]
This m e c h a n i s m g a i n s s u p p o r t f r o m the f o l l o w i n g
observations:
First, a s o l u t i o n of DMS a n d lead ion ( p H 6) a l o n e
w i l l p r o d u c e lead s e l e n i d e o n l y v e r y s l o w l y (of the
o r d e r of s e v e r a l d a y s ) . If a m m o n i u m h y d r o x i d e is
i n t r o d u c e d , t h e r a p i d f o r m a t i o n of lead s e l e n i d e
t a k e s place. T h e c o n c e n t r a t i o n of s e l e n i d e ion w i l l b e
i n c r e a s e d as the p H is i n c r e a s e d d u e to the shift of
the e q u i l i b r i u m d e s c r i b e d i n Eq. [3] a n d [4] to t h e
right. T h e f o r m a t i o n of colloidal s e l e n i u m [5] is i n -
h i b i t e d b y t h e p r e s e n c e of a r e d u c i n g a g e n t ( s o d i u m
sulfite or ascorbic acid). A c o n s i d e r a t i o n of the fol-
l o w i n g o x i d a t i o n p o t e n t i a l s (11) e x p l a i n s this i n -
h i b i t o r y action:
1. S e = - > Se -~ 2 e - Eob = 0.92
2. 2 O H - -~ SOs = ~ SO4 = ~- 2 e - ~- H 2 0 Eob = 0.93
A t u n i t a c t i v i t y sulfite i o n is o n l y a v e r y s l i g h t l y
b e t t e r r e d u c i n g a g e n t t h a n s e l e n i d e ion in a l k a l i n e
solution. H o w e v e r , i n t h e s o l u t i o n s used i n this i n -
v e s t i g a t i o n , t h e c o n c e n t r a t i o n of s e l e n i d e ion is v e r y
s m a l l c o m p a r e d to t h e sulfite ion c o n c e n t r a t i o n a n d
this w o u l d f a v o r o x i d a t i o n of the sulfite i n p r e f e r -
e n c e to t h e selenide. Also, it s h o u l d be n o t e d t h a t
m e t a l l i c s e l e n i u m c a n r e a c t w i t h s o d i u m sulfite to
f o r m s o d i u m s e l e n o s u l f a t e , Na2SeSO3 (12). This w a s
d e m o n s t r a t e d b y the r e a c t i o n of 0.1g s o d i u m sulfite
w i t h 25 m l of a DMS (0.1M) s o l u t i o n t h a t h a d u n -
dergone considerable decomposition. W i t h i n 5 m i n
the red, colloidal s e l e n i u m h a d d i s a p p e a r e d a n d a
colorless s o l u t i o n w a s f o r m e d . Hence, sulfite m a y n o t
o n l y f u n c t i o n as a n o x i d i z i n g i n h i b i t o r , itself f o r m i n g
sulfate, b u t c a n also r e a c t w i t h t h e s e l e n i u m t h a t
m a y be i n i t i a l l y p r e s e n t to f o r m s e l e n o s u l f a t e ion
a n d t h u s p r e v e n t t h e d e p o s i t i o n of red, colloidal
s e l e n i u m . It is a s s u m e d t h a t ascorbic acid f u n c t i o n s
o n l y to p r e v e n t the o x i d a t i o n of t h e s e l e n i d e ion for
it w i l l n o t r e m o v e colloidal s e l e n i u m f r o m d e c o m -
posed DMS.
If the f o r m a t i o n of lead s e l e n i d e is ionic i n n a t u r e ,
t h e r a t e of this r e a c t i o n w i l l be p r o p o r t i o n a l to t h e
c o n c e n t r a t i o n s of t h e l e a d a n d s e l e n i d e ions. T h e s e
c o n c e n t r a t i o n s m u s t be m a i n t a i n e d at v e r y low
v a l u e s , since t h e s o l u b i l i t y p r o d u c t of lead s e l e n i d e
is 10 -ss (13).
SOCIETY January 1964
L e t us n o w c o n s i d e r the m e c h a n i s m b y w h i c h the
a n t i o x i d a n t s i n h i b i t t h e f o r m a t i o n of lead selenide.
T h e r e a c t i o n b e t w e e n a l k a l i n e lead c i t r a t e a n d DMS
w a s m u c h m o r e r a p i d i n t h e a b s e n c e of a r e d u c i n g
agent. A s s u m i n g t h a t t h e r e a c t i o n i n v o l v e s t h e c o m -
b i n a t i o n of t h e ions, the q u e s t i o n arises as to h o w
sulfite ion could r e d u c e the s e l e n i d e or lead ion c o n -
d u c e d if u n d i s s o c i a t e d m o l e c u l e s of lead sulfite w e r e
c o m p l e x is not p r o b a b l e (14). A n a l t e r n a t i v e could
i n v o l v e t h e f o r m a t i o n of a c o m p l e x b e t w e e n sulfite
ion a n d DMS. This w o u l d r e d u c e t h e s e l e n i d e ion
c o n c e n t r a t i o n b y c o m p l e x i n g t h e DMS t h u s i n h i b i t -
ing b o t h the d e c o m p o s i t i o n a n d t h e d e p o s i t i o n r e a c -
tions. T h e v a r i a t i o n in b e h a v i o r of D M S - s u l f i t e
s o l u t i o n s as a r e s u l t of aging' is m o s t p r o b a b l y d u e to
t h e r e d u c t i o n i n sulfite c o n c e n t r a t i o n as it is oxidized
to sulfate. To i l l u s t r a t e this, 0.006g of solid s o d i u m
sulfite w a s a d d e d to a n aged s o l u t i o n of D M S - s u l f i t e
(16 h r ) . T h e r e s u l t i n g r e a c t i o n w i t h lead ion w a s t h e
s a m e as t h a t o b s e r v e d for a f r e s h D M S - s u l f i t e s o l u -
tion, the i n h i b i t o r y effect b e i n g c o m p l e t e l y restored.
T h e a b i l i t y of s e e d i n g n u c l e i to e n h a n c e t h e f o r -
m a t i o n of colloidal gold has b e e n discussed b y
W e i s e r (15). P i c k (3) has d e s c r i b e d t h e use of seed-
ing n u c l e i i n t h e d e p o s i t i o n of lead sulfide films a n d
proposes the f o l l o w i n g m e c h a n i s m to e x p l a i n t h e i r
effect.
First, seeding n u c l e i are a d s o r b e d o n t h e s u r f a c e
o n w h i c h the lead sulfide is to be deposited. T h e s e
n u c l e i t h e n s e r v e as the base to w h i c h lead sulfide
p a r t i c l e s are a t t r a c t e d a n d b e c o m e m o r e a d h e r e n t to
t h e surface. P i c k p o i n t s out t h a t t h e s e e d i n g effect
is g r e a t e s t w h e n t h e s e e d i n g n u c l e i a n d t h e m a t e r i a l
to be deposited is i s o m o r p h o u s .
I n t h e d e p o s i t i o n of lead s e l e n i d e it w a s f o u n d t h a t
p r e c o a t i n g the glass slides w i t h colloidal s o l u t i o n s of
gold, lead iodide, or lead sulfide did n o t i m p r o v e
m i r r o r f o r m a t i o n a n d a c t u a l l y p r o d u c e d m i r r o r s of
poorer quality. A p p a r e n t l y the solutions containing
these sols i n t e r f e r r e d w i t h t h e lead s e l e n i d e d e p o s i -
tion p r o b a b l y b y p r o d u c i n g a n u n d e s i r a b l e s u r f a c e
c o n d i t i o n on t h e glass. I n c o n t r a s t , t h e p r e s e n c e of
s i l v e r ion in t h e d e p o s i t i o n r e a c t i o n r e s u l t e d i n a
m o r e r a p i d m i r r o r deposition. I n this case the f o r m a -
t i o n of silver s e l e n i d e did i m p r o v e t h e q u a l i t y of
the mirror.
T h e most d e s i r a b l e r a t e of d e p o s i t i o n a n d t h e best
r e p r o d u c i b i l i t y i n r e s i s t a n c e as w e l l as m a x i m u m
u n i f o r m i t y and homogeneity in mirror quality were
o b t a i n e d w h e n t h e slides w e r e p r e c o a t e d w i t h col-
loidal lead selenide. This t r e a t m e n t a p p a r e n t l y f u r -
n i s h e d a b e d of n u c l e i w h i c h a t t r a c t e d a n d h e l d lead
s e l e n i d e p a r t i c l e s to t h e s u r f a c e d u r i n g t h e a c t u a l
d e p o s i t i o n reaction.
Manuscript received May 7, 1963.
A n y discussion of this paper will appear in a Discus-
sion Section to be published in the December 1964
JOURNAL.
REFERENCES
1. O. Hauser and E. Biesalski, Chem.-Ztg, 34, 1079
(1910).
2. H. Wilman, Proc. Phys. Soc., 60, 117 (1948).
3. H. Pick, Z. Physik, 126, 12 (1949).
Vol. 111, No. 1 DEPOSITION OF FILMS OF LEAD SELENIDE 47
4. F. Kicinski, Chem. & Ind., 1948, 54. 11. W. M. L a t i m e r , " O x i d a t i o n Potentials," p. 74, P r e n -
5. C. J. Milner and B. N. Watts, Nature, 163, 322 tice H a l l Inc., New York, N. Y. (1952).
(1949). 12. California Research Corp., Brit. 631,464, Nov. 3,
6. R. A. Zingaro, F. C. Bennett, Jr., and G. W. H a m - (1949).
mar, J. Org. Chem., 18, 292 (1953). 13. W. M. L a t i m e r , " O x i d a t i o n Potentials," p. 155,
7. H. B. Weiser, "Inorganic Colloid Chemistry," Vol. 3, P r e n t i c e H a l l Inc., New Y o r k (1952).
p. 113, J o h n W i l e y & Sons, Inc., N e w Y o r k (1938). 14. N. V. Sidgwick, " C h e m i s t r y of the Elements and
8. H. B. Weiser, ibid., Vol. I, p. 32 (1933). Their Compounds," Vol. I, p. 626, U n i v e r s i t y
9. J. Brooks, J. Phys. Chem., 32, 1717 (1928). Press, L o n d o n (1951).
10. M. B o b t e l s k y and B. Graus, J. Am. Chem. Soc., 75, 15. H. W. Weiser, "Inorganic Colloid Chemistry, "Vol. I,
4172 (1953). p. 35, J o h n W i l e y & Sons, Inc., N e w Y o r k (1933).

Luminescent Behavior of the Rare Earths in

Yttrium Oxide and Related Hosts
K. A. Wickersheim 1 and R. A. Lefever 2
Genera~ Telephone and E~ectronics Laboratories, Inc., Palo A~to, California

ABSTRACT
The absorption, excitation, and fluorescence spectra of Y203:Eu a r e p r e -
sented and i n t e r p r e t e d . The high l u m i n e s c e n t efficiency of this m a t e r i a l and
its u n u s u a l p e r f o r m a n c e at e l e v a t e d t e m p e r a t u r e s are discussed. The c o m p a r a -
tive b e h a v i o r of o t h e r r a r e e a r t h s in y t t r i u m oxide and of the r a r e e a r t h s in
certain other oxides of y t t r i u m and l a n t h a n u m are also discussed briefly.

I n c r e a s e d i n t e r e s t in t h e r a r e e a r t h s as f l u o r e s c e n t already completed preliminary studies on the growth

ions h a s r e s u l t e d f r o m solid s t a t e l a s e r studies. T h e
s h a r p n e s s of t h e r a r e e a r t h e m i s s i o n lines a n d t h e
l o n g f l u o r e s c e n c e life t i m e s a r e p a r t i c u l a r l y a t t r a c -
t i v e in t h i s a p p l i c a t i o n . A s a r e s u l t of t h i s s p e c i a l -
i z e d i n t e r e s t in r a r e e a r t h l u m i n e s c e n c e for l a s e r a p -
plications, optically perfect and physically hardy
c r y s t a l s of m a t e r i a l s n o t p r e v i o u s l y e m p l o y e d as
hosts for t h e r a r e e a r t h s a r e c u r r e n t l y of c o n s i d e r -
able interest.
For several years we have pursued an exploratory
program concerned with the growth and properties
of s i n g l e c r y s t a l m e t a l oxides. G i v e n t h e p r o b l e m of
d e s i g n i n g a n o p t i m u m l a s e r m a t e r i a l , w e d e c i d e d to
i g n o r e at t h e o u t s e t t h e c o n s t r a i n t i m p o s e d b y t h e
c u r r e n t a v a i l a b i l i t y of c r y s t a l s a n d to first s e l e c t or
design a material which met the more fundamental
requirements. Thus we looked for oxides (either
simple or complex) having desirable optical and
mechanical properties, which would accept the tri-
v a l e n t r a r e e a r t h s w i t h o u t p r o b l e m s of ion size or
c h a r g e . A t t h e s a m e t i m e , w e l o o k e d for hosts w i t h
r a r e e a r t h sites of e x c e p t i o n a l l y l o w s y m m e t r y in
t h e h o p e of i n c r e a s i n g t h e p r o b a b i l i t y of r a d i a t i v e
transitions (within the 4f-electron shell) through
d e s t r u c t i o n of p a r i t y f o r b i d d e n n e s s . It w a s also
hoped that hosts would be found where competing
(e.g., n o n r a d i a t i v e ) r e l a x a t i o n p r o c e s s e s w o u l d b e
m i n i m i z e d , a l t h o u g h ( e x c e p t for s e l e c t i o n of m a t e -
rials with low frequency lattice vibrations) we
k n e w of no d i r e c t m e a n s of c o n t r o l l i n g t h i s p a r a m -
eter. Of t h e o x i d e s c o n s i d e r e d , c o m p o u n d s h a v i n g
t h e y t t r i u m o x i d e s t r u c t u r e a p p e a r e d b e s t to m e e t
t h e m a j o r i t y of t h e specified r e q u i r e m e n t s . 3 W e h a d
1 Present address: D e p a r t m e n t s of Materials Science and Electri-
cal E n g i n e e r i n g , S t a n f o r d U n i v e r s i t y , S t a n f o r d , C a l i f o r n i a .
Present address: Sandia Laboratory, Albuquerque, New Mexico.
F o r c r y s t a l l o g r a p h i c d a t a , see rcf. (1).
(2) a n d o p t i c a l p r o p e r t i e s (3) of t h i s m a t e r i a l a n d
f e l t t h a t it o f f e r e d p r o m i s i n g p o s s i b i l i t i e s .
A f o r t u i t o u s a s p e c t of t h e r e s u l t i n g w o r k w i t h
r a r e e a r t h s in y t t r i u m o x i d e w a s t h e d i s c o v e r y of
strong, broad absorption bands which could be uti-
l i z e d f o r e x c i t a t i o n of c e r t a i n of t h e ions. A l t h o u g h
t h e s e b a n d s o c c u r in t h e u l t r a v i o l e t , t h e y a r e in
s o m e i n s t a n c e s w e l l l o c a t e d for efficient e x c i t a t i o n
b y c o n v e n t i o n a l u l t r a v i o l e t sources.
General considerations.--The s h a r p - l i n e e m i s s i o n
a n d a b s o r p t i o n s p e c t r a of t h e r a r e e a r t h ions in
solids h a v e i n t r i g u e d s p e c t r o s c o p i s t s f o r y e a r s . 4 O u t
of t h e d e t a i l e d s t u d i e s of t h e s e s p e c t r a h a s c o m e a
r a t h e r c o m p l e t e u n d e r s t a n d i n g of t h e f - e l e c t r o n
e n e r g y l e v e l s of t h e m a j o r i t y of t h e t r i v a l e n t r a r e
e a r t h s , i n c l u d i n g , in m a n y i n s t a n c e s , t h e i r d e t a i l e d
d e p e n d e n c e on c r y s t a l l i n e e n v i r o n m e n t . S o m e w h a t
less w e l l u n d e r s t o o d a r e t h e r u l e s g o v e r n i n g i n t e n s i -
t i e s of t r a n s i t i o n s b e t w e e n f - e l e c t r o n levels. S t i l l
less w e l l u n d e r s t o o d a r e t h e n a t u r e of t h e m o r e
h i g h l y e x c i t e d s t a t e s of t h e s e ions in solids, t h e n a -
t u r e of t h e v a r i o u s e n e r g y t r a n s f e r m e c h a n i s m s
u t i l i z e d in t h e e x c i t a t i o n of fluorescence, a n d t h e
d e t a i l s of p r o c e s s e s i n v o l v e d in n o n r a d i a t i v e r e l a x -
ation.
I n t h e f r e e ion, e l e c t r i c d i p o l e t r a n s i t i o n s b e t w e e n
f-electron levels are strictly forbidden by parity
c o n s i d e r a t i o n s . H o w e v e r , such t r a n s i t i o n s (as w e l l
as o c c a s i o n a l m a g n e t i c d i p o l e t r a n s i t i o n s ) a r e o b -
s e r v e d to o c c u r w e a k l y in solids. This is i n t e r p r e t e d
in t e r m s of e i t h e r s t a t i c or d y n a m i c b r e a k d o w n of
parity. Nonradiative processes, which compete with
t h e r a d i a t i v e p r o c e s s e s in d e t e r m i n i n g f l u o r e s c e n t
efficiency, d e p e n d o n t h e f r e q u e n c y of a v a i l a b l e l a t -
t i c e v i b r a t i o n s a n d t h e e f f e c t i v e n e s s of t h e i r c o u p -
4 T h e l i t e r a t u r e o n this s u b j e c t is e x t e n s i v e . F o r a g e n e r a l d i s -
c u s s i o n , g i v i n g r e f e r e n c e to t h e m a j o r i t y of t h e p r i n c i p a l c o n t r i b u -
t o r s t o t h e field, s e e ref. (4), e s p e c i a l l y pp. 453-476.