ULTRASONIC STUDIES OF THE POLYMER STRUCTURE OF THE CHALCOGENIDE GLASSES

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ULTRASONIC STUDIES OF THE POLYMER STRUCTURE OF THE CHALCOGENIDE GLASSES

V. Ratobylskaja, L. Simonova

To cite this version:

V. Ratobylskaja, L. Simonova. ULTRASONIC STUDIES OF THE POLYMER STRUCTURE OF THE CHALCOGENIDE GLASSES. Journal de Physique Colloques, 1981, 42 (C4), pp.C4-955-C4-958.

�10.1051/jphyscol:19814209�. �jpa-00220837�

CoZloque C4, suppZdment au nO1O, Tome 42, octobre 1981 page C4-955

ULTRASONIC STUDIES OF THE POLYMER STRUCTURE OF THE CHALCOGENIDE GLASSES

V.A. R a t o b y l s k a j a and L.A. Sirnonova

MendeZeev I n s t . Chem. TechnoZogy, Moscou, U . S . S . R.

Abstract.- The r e s u l t s of u l t r a s o n i c investigations of v i t r e o u s chalcogenide semiconductors a r e r e p o r t e d i n t h e temperature range ~ O - T ~ O C . On t h e b a s i s of t h e observed e f f e c t s of t h e i n f l u e n c e 01' t h e g l a s s thermal p a s t on t h e temperature dependence of t h e v e l o c i t y and t h e ultrasound a b s o r p t i o n t h e conclusion has been drawn about of polymer s t r u c t u r e of v i t r e o u s A s S and A s Se and s t r u c t u r a l

2 3 2 3

d i i ' f e r e n t i a t i o n i n them a s well.

I n t r o d u c t i o n . - Homoatomic chalcogenlaes a s well a s t h e i r a r s e n i c compounds e x h i b i t some s i m i l a r i t y t o organic polymers.

Tarasov [l] proposed t h a t c r y s t a l l i n e ana g l a s s y As S r e r e loolced 2 3

upon a s a c h a i n - l i k e s t r u c t u r e according t o t h e r e s u l t s of s p e c i f l c heac. The chain-like polymer s t r u c t u r e c o n s i s t s of a screw chain with s t r o n g bonds As-S forming an i n t e r m e d i a t e sp3 hybrid and a r a t h e r weak a d d i t i o n a l As-S bond between each chain. The presence of chain f e a t u r e s i n t h e polymer network As2S3 s u g g e s t s t h e r e s u l t s of thermo-mechanical investigationsC21. Examining t h e r e s u l t s of v i s c o - e l e s t i c p r o p e r t i e s i n v i t r e r ' i c a t i o n range, Eisenberg and o t h e r s

C33

have deduced t h a t t h e samples of A s s 4 r e v e a l t y p i c a l f e a t u r e s f o r organic l i n e a r polymers.

Xxperimental r e s u l t s and d i s c u s s i o n s . - Glasses on As,S and A s Se 2 3

w i t h d i f f e r e n t thermal p a s t were taken a s t h e s u b j e c t of t h i s ² 3 r e s e a r c h . The measurments of t h e p r i n c i p a l parameters, t h e v e l o c i t y and t n e u l t r a s o u n d a b s o r p t i o n were performed according t o t h e reso- nance method a t one frequncy equal t o 136 kc on t h e l o q i t u d a n a l waves, t n e h e a t i n g range being Z O - T ~ ~ C . The r e s u l t s of t h i s measur- ments a r e given in Table. Temperature dependence of u l t r a s o n i c a b s o r p t i o n expressed i n terms of r e v e r s e v a l u e s of r e l i a b i l i t y Q-IT) and resonance rrequency r / f o ( T j f o r * A S ~ S and AszSe3 a r e given a s

3

Article published online by EDP Sciences and available at http://dx.doi.org/10.1051/jphyscol:19814209

C4-956 JOURNAL DE PHYSIQUE

a n example in Figures 1,2 and' 3.

Material bf /oT,

'l'

ⁿ

m

.

^sec-' I { Z * ~ C - " 'C m sec-?

Data of ultrasound i n v e s t i g a t i o n s prove low e l a s t i c i t y in t h e polymer network of' a r s e n i c t r i s u l f i d e and a r s e n i c triseleni.de g l a s s e s The v e l o c i t y of t h e u l t r a s o n i c v i b r a t i o n i s c l o s e t o t h a t of poly- styrene and amounts t o 224Q-1910 m.per.sec. Temperature c o e f f i c i e n t of t h e sound v e l o c i t y has usual negative value f o r a l l g l a s s e s involved. The sound absorption i n t e n s i t y i s observed i n t h e high- temperature range rrom ,180 t o 2b0°c f o r As2S and , 1 7 ~ - 2 7 0 ~ ~ 3 f o r As2Se3. The peak i n t e n s i t y i s high and i s resolved i n terms of t h e d a t a r / f o ( T ) . The maxima p o s i t i o n of u l t r a s o n i c absorption coincides with sor'tening ranges or t h e i n v e s t i g a t e d g l a s s e s and t h a t ' s why they can be r e f e r r e d t o t h e main d - r e l a x a t i o n process accounting f o r t h e t r a n s i t i o n of v i t r i f i c a t i o n

-

sortening. For A s S nigh-

2 3

%

temperature branch of oC peak -coo

a t T 7 2 7 0 ' ~ lowers t o t h e l e v e l of l o s s e s f o r v i t r i f i e d s t a t e

-L?# ( Q " = ~ * I O ' ~ ) and t h e n appears

on t h e p l a t o .

Quantative estimation of t h e

0.6 equilibrium modulus of t h e molecular weight of polymer

-Q4 chain s e c t i o n behveen two cross- l i n k i n g s i s equal t o

--

,l 6300 g *mol-l

,

which corresponds t o 130 base units f o r As2S3.

H i g h e l e s t i c s t a t e e x h i b i t s

t P

'S s o -

zo

10

-

-"-.."-.S\-'

"-

%# ^-*\

\

izo -

-

40

ZOO n o m

-

^{.. ...}

^--...S.

^.A

⁰

^{....*. . J'} i ⁱ

o ^{100 ZOO}

Jbo

7&l i t s e l f moreslightly i n As2Se

3

rLg. 1

.

^{As2S3 (} 700°c-l Oh) and i t s t r a n s i t i o n i n t o p l a s t i c

A l l t h e s e f a c t s prove t h a t A s S and A s Se show e s s e n t i a l dii'fe-

2 5 2 3

r e n c e s I n t h e n p o l p e r s t r u c t u r e . V i t r e o u s As2S3 i s an i n o r ~ a n i c c h a i n - l i ~ e p o l y n e r . Vltr-cous A s Se 1s a rigid, three-dimensional

2

3

p o l y n e r : n t h loosely-packed a t o n s .

A 1 1 t h e d a t a o b t a l n e u l n a i c a t e t h e t l l e r n a l pas* of g l a s s

.*S a..--

... _...

'fii.

..

60

.S.

....

...

. J

.. ...L... .,...'

100 200 300 T ('C)

-

f2, k ' i 2 . 2 ; The ternpereture

.(I uependence of t h e

resonance xrequ.ency

-0.80 and u l t r a s o l n c

a b s o r p t i o n f u r As2Y3

-0.60

( 200'~-20h)

-a40

0.20

~ ' l g . 3: As2Se3 ( 7 3 0 ~ ~ - 1 0 h ) It's q u i t e n a t u r a l t o a t t r i b u t e i n f l u e n c e s on Ghc v e l o c i t y ana uLtrasound. a b s o r ~ t i o n . In t h e r m a l l y t r e a t e d As S (200'~-20h)

2 3 -relaxation t r a n s i t i o n i s of uouble c n a r a c s e r

.

The second t r a n s l t l o n e x i s t e n c e above IT,. o c e u r s I n o r g a n i c

t

polymers m d i s u s u a l l y accounted f o r by t h e a v a i l a b i l i t y of r e g u l a r c r y s t a l s e c t i o n s o r t h e C r a n s i t l o n ot' one amorphous s t a t e i n e o t n e

0

0 -

'"

10

0

... .- ... ^{^}

.

^-

'/f, ,.,' ^'

,.

_,

W o

,

'l\

f2C BO

40 _{0 "}

1

300 TI'CI

-

-

_L \\ "..-,

i

Q-'

, i

.._.-.

...

loo ZOO 3bo T ~ C )

fh

o t h e r one.

lll0 The a n a l y s i s of t h e o b t a i n e d

e x p e r i m e n t a l d a t a about t h e

, i n f l u e n c e of thermotreatment on t h e F2 peak i n t e n s i t y a l l o v ~ u s t o s u g g e s t t h a t t h e second high-

- 4 6 t e m p e r z t u r e t r a n s i t i o n i n A s 2 S 3 r e f l e c t s t h e s t r u c t u r a l d i f f e - r e n t i a t i o n of t h e polymer n e t -

0.4 work A s 3 A s X-ray s t r u c t u r a l 2 3'

i n v e s t i g a t i o n s do'not r e v e a l t n e .gz t r a c e s of c r y s t a l phase it

should be a d m i t t e d t h a t t h e o r d e r i n g i n A s S netv;ork i s due

2 3

t o t h e a n t i - c r y s t a l l . i n e c l u s t e r s .

C4-958 JOURNAL DE PHYSIQUE

the transition at T = ~ o ~ O C to "unfreez~ng" of mobility in random As S ranges, and the transition at ~ = 2 3 5 O ~ to "umt'reezing" of

2

3

mobiLity inslde the clusters. :;/hen changlng S-Se the trend to the differentiation of network is lost.

It should be iuerred that the observed differences In the polymer structure As S and As2Se are closely connected mlth

2 3 3

chalcogenide steriochemistry. Due to above steriocnemica~ features the trarlsitlon bonds As-Se-As are less mobile, and this results proves to the formation of more rigid As Se network.

2 3

Conclusion.- In terms of the above investigations, it is possible to draw a conclusion that in chalcogenide glasses as well as in organic polymers the features of polymer structures and structural changes are greatly pronounced at above To when there are conditions for "unfreezing" of relaxation processes at different; molecular e;

levels. The mobility in large units manifests itself as h g h -

elastisity erfect. In the range of higheiastisity practically almost equal defrormation is observed and. this testisies to the fact that arsenic chalcogenides are of network nature. The most pronounced similarity to organic polymers can be observed m arsenlc trisuli'ide glass.

References.- '1. 'l'arasov V.V. ,Problems in the physics of glass, Stroiisdat Publishers ,Lloscow (19'19) in Husslan.

2. Tarasov V.V.,Bartenjev G.M.,hkemeeva A.S.,Ratobylskaja V.A., The Vitreous State.Proc.02 a confer.on the vitreous state,Ac.Sci.

USSR ,Moscow-Leningrad ('l 963) 167.

3.

Eisenberg A.,Saito S.,Teter L.A.,Transitions and relaxations in polymers,American Chemical Society Symposium,Mew Jersey (1965)

359.