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Dangling-bond and void-like structure in amorphours semiconductors

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1985 Chinese Phys. Lett. 2 533

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 CHINESE PHYSICS LETTERS
CHINESE PHYS. L E T T . Science Press, Beijing
V 0 1 . 2 , No.12(1985) Springer-Verlag

DANGLING-BOND AND V O I D - L I K E STRUCTURE I N AMORPHOURS SEMICONDUCTORS

WU X i a n g , CHEN Hong
% % % i J 3
( P o h l - I n s t i t u t e of S o l i d - s t a t e P h y s i c s , T o n g j i U n i v e r s i t y ,
Shanghai )

(Received 1 7 J u l y 1985)

T o expZain the differences i n properties between the chaZcogenide

gZassy semiconductors and the tetrahedrally-bonded semiconductors,
a microscopic structural model is given i n t h i s Zetter. Based on
t h i s model, we can not onZy get two-ZeveZ systems, negative-U pairs,
and the Urbach rule, but aZso account f o r some recent experiments.
It has been shown experimentally that t h e r e are s h a r p d i f f e r e n c e s
in properties between t h e c h a l c o g e n i d e g l a s s y semiconductors (CGS) and
t h e tetrahedrally-bonded amorphous s e m i c o n d u c t o r s (TAS)
1 . Though several
models, e . g . , two-level s y s t e m ( T L S ) m o d e 1 2 ' 3 , n e g a t i v e - U p a i r model4 a n d
conf i g u r a t i o n a l - c o o r d i n a t e model5 , have b e e n p r o p o s e d t o e x p l a i n t h e s e
d i f f e r e n c e s from d i f f e r e n t p o i n t s of view, some p r o b l e m s a r e s t i l l un-
solved. F i r s t l y , a l l t h e s e models a r e p h e n o m e n o l o g i c a l and t h e m i c r o s -
c o p i c f e a t u r e s are not c l e a r . S e c o n d l y , e a c h of t h e models c a n e x p l a i n
o n l y one o r two d i f f e r e n c e s o f p r o p e r t i e s between CGS a n d TAS. The p r o -
blem h a s b e e n c o n s i d e r e d by some a u t h o r s r e c e n t l y
6
. The a i m of t h i s l e t -
ter i s t o i n t r o d u c e a microscopic s t r u c t u r e model, c a l l e d dangling-bond
and v o i d - l i k e structure (DVS) model. S t a r t i n g w i t h DVS, w e have f o u n d
the c o n n e c t i o n between t h e phenomenological models. Some a p p l i c a t i o n s
of DVS t o r e c e n t e x p e r i m e n t s a r e a l s o g i v e n .
DVS and TLS: D a n g l i n g bonds a n d v o i d - l i k e s t r u c t u r a l d e f e c t s are two
structural characteristics i n amorphous s e m i c o n d u c t o r s . L e t us c o n s i d e r
a v o i d w i t h some d a n g l i n g bo'nds on i t s s u r f a c e , a n d i m a g i n e f u r t h e r t h a t
i n s i d e t h e void t h e r e is a " w e a k l y bonded" atom ( o r c l u s t e r of atoms),
which i n t e r a c t s w i t h t h e e l e c t r o n s o f d a n g l i n g b o n d s .
For s i m p l i f i c a t i o n , w e c o n s i d e r a n atom A i n t e r a c t s w i t h two d a n g l i n g
bonds. The H a m i l t o n i a n f o r DVS i s

H ~ ~1 1~ = 1
( E . ~ . + ~ i ~ i a ~ i - u ) + ( E oN ~ ~ + u ~ 1
N (~V d ~i a . aNo+d a~i a + ~H . c~) +
1 d i Ud

+ (-+
P* 1 + +
R 2 Q 2 ) - M ( aos aop +aopaos ) Q - D ( NR-NL 1Q ,
olQ+-m
2 A (1)
2mA

where i = L , R ; U= I.,+;
+
d = s , p ; Nod=aodaod, N . = a a iu, . =N i u + N i - u * The terms
N1
i n eq.( 1)c o r r e s p o n d , r e s p e c t i v e l y , t o ( 1 ) t h e e l e c t r o n i c e n e r g y o f dang-
l i n g bonds, ( 2 ) t h e e n e r g y of t h e e l e c t r o n i c s h e l l of atom A , (3) the
hoppingof e l e c t r o n s between t h e d a n g l i n g bonds a n d t h e e l e c t r o n i c s h e l l
 534 C H I N E S E PHYSICS LETTERS Vo1.2, No.12

of atom A , ( 4 ) t h e v i b r a t i o n a l e n e r g y of t h e i o n of A, ( 5 ) the coupling

of t h e e l e c t r o n i c s h e l l t o t h e i o n of A, ( 6 ) t h e c o u p l i n g of t h e e l e c -
t r o n s of d a n g l i n g bonds t o t h e i o n of A . Using t h e G r e e n ' s f u n c t i o n m e -
thod, w e f i n d , by H a r t r e e - F o c k a n d a d i a b a t i c a p p r o x i m a t i o n , t h a t atom
A w i l l meet w i t h a n e f f e c t i v e p o t e n t i a l V ( Q ) . The s h a p e of V e f f ( Q )
ef f
depends on two d i m e n s i . o n l e s s p a r a m e t e r s x and y . I n parameter space,
w e f i n d t h a t t h e r e are two p h a s e s , corresponding t o t h e double-well and
the single-well potentials, respectively ( f i g . 1 ) .

hase

2?
L
0
1
II y-1
Fig.1 Fig.2
The p a r a m e t e r s of t h e e f f e c t i v e d o u b l e - w e l l p o t e n t i a l are as follows
(fig.2):

with
e = / M(< N , + > - < N , - > ) 1+ I D(<NR>-<NL> ) 1, (3)
+
where NOlt=a,?a o k , and a,, is related t o athrough a u n i t a r y transforma-
od
tion. From f i g . 2 , w e c a n g e t a TLS, which i s t h e o r i g i n of t h e anomalous
I
t h e r m a l and u l t r a s o n i c b e h a v i o r s of g l a s s e s .
Fig.1 is very i m p o r t a n t f o r u s t o u n d e r s t a n d t h e d i f f e r e n c e of t h e r -
m a l a n d u l t r a s o n i c p r o p e r t i e s between CGS a n d TAS. R e c e n t l y , Graebner
a n d A l l e n f o u n d t h a t i n a-Ge, t h e d e n s i t y of s t a t e s of TLS d e c r e a s e s w i t h
i n c r e a s i n g d e n s i t y of t h e m a t e r i a l
8
. T h i s c a n be e x p l a i n e d by f i g . 1 .
Following P h i l l i p s ' a p p r o x i m a t i o n 3 , w e o b t a i n t h e d e n s i t y of s t a t e s
of T L S a s

i n a - S i 0 2 was c a l c u l a t e d as
The m a g n i t u t e o f A A . %0.5K, which
min ii min
agrees with tha experimental data.
V01.2, No.12. WU X i a n g , e t a l . 535

DVS a n d N e g a t i v e - U p a i r s : A s s u m i n g t h a t t h e a t o m A can t u n n e l t h r o u g h
a double-well p o t e n t i a l , w e c a n rewrite e q . ( l ) i n t h e form of a t o m i c t u n -
n e l i n g s t a t e s and t h e i r c o u p l i n g w i t h e l e c t r o n s . After unitary trans-
1
formation, we f i n d

where Ne and N a r e t h e o c c u p i e d number o p e r a t o r s o f t h e e x c i t e d s t a t e

g
a n d t h e g r o u n d s t a t e o f TLS, r e s p e c t i v e l y , satisfying the relation
N + N = l . The e i g e n e n e r g y o f e q . ( 7 ) i s
e g
EDVS=EDVS(NL, N e , NR). (8)

N. (i=L, R) can take three values 0, 1 and 2 , which represent three

1
9
c h a r g e d s t a t e s Di (q=+, 0, - ) of a d a n g l i n g bond. Ne can t a k e t w o values
0 a n d 1, c o r r e s p o n d i n g two s t a t e s A ( s = g , e ) o f a TLS. So EDVS c a n t a k e
S
q
e i g h t e e n d i f f e r e n t v a l u e s w i t h d i f f e r e n t s t a t e s @ ( D L , A s , D:'). The s i g n
of Uzff d e p e n d s on t h e c o u p l i n g o f electrons with atomic tunneling
states. Uyff >O f o r weak c o u p l i n g : UFff<O f o r s t r o n g coupling; and t h i s
results i n negative-U pairs. The d i f f e r e n t p r o p e r t i e s of ESR o b s e r v e d
c a n be e x p l a i n e d b y t h e a s s u m p t i o n t h a t U:ff>O i n TAS a n d U e i f f < O i n CGS.
The eff
s i g n o f ULR a l s o d e p e n d s on t h e c o u p l i n g o f e l e c t r o n s w i t h a t o m i c
t u n n e l i n g states. E q . ( 7 ) i s a n a l o g o u s t o a valence a l t e r n a t i o n p a i r (VAP)
for qif = 0 , a n d t o a n i n t i m a t e VAP f o r U>:;' 0, When ,:if< 0, we get
a n o t h e r k i n d o f VAP ( a n o m a l o u s VAP).
Recently, Fox e t a l . have found t h a t i r r a d i a t i o n of a-As2S3 with
band-edge a t T < l K c a n n o t o n l y c r e a t e m e t a s t a b l e ERS, b u t a l s o
photons
open a m e t a s t a b l e gap i n N
TLS
(E)9 .
T h i s phenomenon c a n b e e x p l a i n e d i n
t h e f r a m e o f DVS. Under t h e e x c i t a t i o n o f p h o t o n s , a DVS w o u l d t r a n s f e r
from O(DL,
+ As, DR) t o
+
@(DL,As, D i ) or @(Di, As, D R ) . Such t r a n s i t i o n s
w i l l l e a d t o ERS a n d t h e c h a n g e of The l a t t e r r e s u l t s i n ' a cJap i n
A , ~ ~ .
NTLs(E) (See e q . ( 4 ) )

A E =minfexp+i-
A~ (2MD+3D)]-l}.
A
Using experimental data, s u c h as g l a s s - t r a n s i t i o n t e m p e r a t u r e a n d Debye
temperature, we g e t AEQlOGHz f o r a-AsZS3, which a g r e e s w i t h t h e e x p e r i -
m e n t a l r e s u l t AE*5GHz.
DVS a n d t h e U r b a c h R u l e : The g r o u n d s t a t e s o f DVS, i n CGS, consist
of E+ a n d D - , which have double-well s t r u c t u r e i n configurational space
b e c a u s e of t h e i r s t r o n g c o u p l i n g s t o TLS. A t low t e m p e r a t u r e , the opti-
c a l t r a n s i t i o n s b e l o w f o r b i d d e n g a p Eg a r e f r o m v a l e n c e b a n d E V t o 'D ,
and from D - t o c o n d u c t i o n band E c , which l e a d t o a n o p t i c a l a b s o r p t i o n
c o e f f i c i e n t w r i t t e n as
536 CHINESE PHYSICS LETTERS V01.2, No.12

a ( f i u ) = o . exp [ ($u-Eg)/2kBT*l , (10)

eq.(lO) agrees with the experimental result known as the Urbach rule.
Recently, Kolobov et al. suggested that the Urbach rule should be ex-
plained in a configurational-coordinate model 5 .
But the reason why there
exist some NH -like electronic structures in CGS, which was the main as-
3
sumption of ref.5, is not clear.
Experiments showed that the Urbach edge would shift under the in-
fluence of an external field, known as photodarkening’’ and phonobleach-
ing” phenomena. These phenomena can be understood in present model.
In addition, based on DVS, we predict that the photodarkening shift of
Urbach edge varies linearly with hydrostatic pressure and increases with
glass-transition temperature, which agrees well with experiments 10,12

REFERENCES
1. CHEN Hong and WU Xiang, Commun. in Theor.Phys.4(1985)281.
2. P.W.Anderson, B.I.Halper11-1and C.M.Varmar, Philos.Mag.25(1972)1.
3. W.A.Phillips, J.Low Tem.Phys.7(1972)351.
4. P.W.Anderson, Phys.Rev.Lett.34(1975)953.
5. A.V.Kolobov and O.V.Konstantinov, Phil.Mag.B47(1983)1.
6. M.I.Klinger and I.I.Yaskovets, J.Phys.C 17(1984)L949.
7. CHEN Hong and XU Xiang, Commun-in Theor.Phys.3(1984)275; ibid, 3
(1984)423.
8. J.E.Graebner and L.C.Allen, Phys.Rev.Lett.51(1983)1566.
9. D.L.Fox, B.Golding and W.H.Haemmerde, Phys.Rev.Lett.49(1982)1356,
10. K.Tanaka, Phys.Rev.B30(1984)4549.
11. Suzuki, S.Okano, H.Nagaoka and T.Hata., J.Non-Cryst.Solids, 35/36
( 1980)1067.
12. K.Kimura, H.Nakata, K.Murayama and T.Nimomiya., Solid State Commun.
40(1981)551.