JOURNAL DE PHYSIQUE ColZoque C8, supplBmeni: au n08, Tome 41, aoCt 1980, page Cg-218

X-RAY DIFFRACTION STUDY ON L I Q U I D AND NON CRYSTALLINE SOLID GALL1 UP?, B l SYUTH AND PIERCURY

A. Bererhi, A. ~ i z i d * , L. Bosio, R. Cortes, A. Defrain and C. Segaud

Groupe de Recherche n04 du CNRS "Physique des Liquides e t Electrochimie", assoeie' ri

l'llniversitd Pierre e t Marie Curie, 4 place Jussieu, 75230 Paris Cbdes 05, France.
*Universite' deTunis, Facult6 des Sciences, Ddpartement de Physique, Campus Universitaire
1006 Le Belvdde're, Tunis, Tunisie.

Abstract.- An attempt is made to compare the structures deduced from X-ray measurements on some
pure metals, both in the liquid and the non crystalline state. With Ga and Bi, the liquid and the
amorphous solid structures show some similarities and seem to be correlated with the solid phase
which occurs when crystallisation takes place. Different behaviour is found with Hg : the liquid
structure factor differs from the structure factor in the amorphous state whose main peak is
symmetric in form.

INTRODUCTION r i d e monochromator i n t h e d i f f r a c t e d beam. The

The p r o p e r t i e s of most o f t h e l i q u i d metals r a d i a t i o n s were CuKa and NoKa. By d i v i d i n g t h e sam-

have been s u c c e s s f u l l y described by a hard sphere p l e i n t o small d r o p l e t s , i t was p o s s i b l e t o study

d e s c r i p t i o n i n c o n j o n c t i o n w i t h p e r t u r b a t i o n tech- t h e s t r u c t u r e o f supercooled l i q u i d s : f o r Cia and
Hg t h e d i s p e r s i o n s were prepared by using an u l t r a -
niques [I].
Concerning t h e non c r y s t a l l i n e s o l i d
sonic generator t o disperse t h e molten metals w i t h i n
s t a t e , t h e dense random packing o f hard spheres[2]
i s apparently a s a t i s f a c t o r y approach t o model 1ing e t h y l alcohol s a t u r a t e d w i t h sodium o l e a t e , thus

atomic arrangements i n metal 1i c glasses. However, a1 l o w i ng experiments under t h e normal me1ti ng p o i n t

these d e s c r i p t i o n s completely f a i l when c r y s t a l l i -
s a t i o n does n o t form c l o s e packed s o l i d s ; i n these
cases, t h e l i q u i d s t r u c t u r e f a c t o r o f t e n has a
shoulder o r a hump on t h e high-angle s i d e o f t h e
p r i n c i p a l peak and, i n amorphous s t a t e , n e i t h e r t h e
s t r u c t u r e f a c t o r nor t h e p a i r c o r r e l a t i o n f u n c t i o n
show t h e c h a r a c t e r i s t i c s p l i t t i n g o f t h e second
a t supercooling o f 140 and 61 K r e s p e c t i v e l y ; f o r
B i , t h e procedure o f forming d r o p l e t s t o achieve
l a r g e supercooling [41 was n o t convenient f o r X-ray
i n v e s t i g a t i o n because o f extraneous Braggs peaks
provided by the oxyde-coated drop1 e t s : t h e d i sper-
sions were prepared by shaking t h e molten B i i n
hexadecanol w i t h some s t e r o l s as s u r f a c t a n t s , t h e

max imum . maximum supercooling was thus l i m i t e d t o 68 K.

The present paper describes t h e t y p i c a l beha-
v i o u r of t h r e e o f these metals (namely Ga, B i and
Hg) which o f f e r t h e experimenters t h e unique oppor-
t u n i t y o f i n v e s t i g a t i n g by X-ray d i f f r a c t i o n mea-
surements t h e s t r u c t u r e ( i ) o f t h e normal and su-
percooled l i q u i d , ( i f ) of t h e amorphous s o l i d Pre-
pared by vapour d e p o s i t i o n onto substrates cooled
a t very low temperature.
EXPERIMENTS
An X r a y s diffractometer o p e r a t i n g i n a symne-
t r i c a l r e f l e c t i o n mode has been used t o determine
t h e s t r u c t u r e o f b o t h l i q u i d and amorphous s o l i d
metals.
The experimental arrangement f o r t h e measure-
ment o f t h e s c a t t e r e d i n t e n s i t i e s by l i q u i d s consis-
t e d o f a t h e t a - t h e t a d i f f r a c t o m e t e r [31 w i t h a sta-
t i o n a r y , h o r i z o n t a l sample and a bent l i t h i u m f l u o -
I n a l l cases, samples were cooled o r heated
in VaCUUum chamber i n which t h e pressure could be
reduced torr except f o r Hg where t h e cham-
b e r was f i l l e d w i t h helium [51.
Nominally pure amorphous metals a r e o n l y avai -
l a b l e by vapour d e p o s i t i o n onto l i q u i d helium c o o l d
s u b s t r a t e s [21 : the low temperature condensation
apparatus, c o n s i s t i n g ofan i o n i c u l t r a - h i g h vacuum
system w i t h an e l e c t r o n gun and a l i q u i d helium
c r y o s t a t , i n c o n j u n c t i o n w i t h t h e X-ray d i f f r a c t o m e -
t e r b u i l t on t h e pumping system, has been described
elsewhere [61 ; t h e o n l y m o d i f i c a t i o n s consisted i n
t h e use o f a post-specimen monochromator and a spe-
c i a 1 device f o r mercury d e p o s i t i o n .
Though t h e y were t h i n ( r e s p e c t i v e l y 3, 0.2 and
0.1 pm For Ga, B i and Hg) t h e amorphous f i l m s were
t h i c k enough f o r X-ray d i f f r a c t i o n study. Three

Article published online by EDP Sciences and available at http://dx.doi.org/10.1051/jphyscol:1980856

1

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2 4 6 8 10 -

ilqur. 5 Pal- c l v . l r r l a funcllon for , l o u l d and aorawr IIINUI

c8-220 JOURNAL DE P H Y S l Q U t

wavelengths were used, CrKa, CuKa and MoKa, t o ob- f r e e z i n g occurs i n supercooled l i q u i d Ga i t i s r a -
t a i n r e l i a b l e d a t a i n t h e low and h i g h wavevector t h e r t o t h e metastable @-phase whereas t h e normal
q = 4nsine/X and a l s o t o t a k e advantage of t h e s t a b l e form has always been observed t o occur when
wavelength dependence o f X-ray absorption. c r y s t a l l i s a t i o n takes p l a c e i n supercooled l i q u i d
Hg and B i ; moreover, some authors used t h e c r y s -
RESULTS AND DISCUSSION t a l l i n e l a t t i c e as a framework f o r d e s c r i b i n g li-
q u i d Ga 181, B i 191 and Hg [5, 101 by a quasi
The s t r u c t u r e f a c t o r S(q) o f l i q u i d Ga, B i and
c r y s t a l l i n e s t r u c t u r e model : t h e y a l l e s t a b l i s h a
Hg are shown i n F i g . 1, 2 and 3. Both Ga and B i
e x h i b i t a shoulder on t h e r i g h - a n g l e s i d e whereas close correspondence between the l i q u i d and corres-

Hg o n l y shows a hump ; i n Ga, t h e shoulder gradual- ponding c r y s t a l l i n e s o l i d s t r u c t u r e .

l y increases when t h e temperature i s lowered b u t i n The sane conclusions may be transposed t o t h e

Hg and B i these anomalies remain unchanged though n o n - c r y s t a l l i n e s o l i d Ga and B i : i n amorphous
they a r e l e s s e v i d e n t a t h i g h temperature because s t a t e these two metals show e v i d e n t resemblances t o
o f the broadening o f t h e f i r s t maximum. The most t h e corresponding l i q u i d b o t h i n s t r u c t u r e f a c t o r s
n o t i c e a b l e e f f e c t o f t h e temperature on t h e s t r u c - ( F i g . 1 and 2) and i n p a i r c o r r e l a t i o n f u n c t i o n s
t u r e f a c t o r s i s t h e damping i n h i g h q range and t h e ( F i g . 5 and 6) ; because o f t h e absence o f d i f f u -
r e d u c t i o n o f t h e f i r s t peak h e i g h t S(qo) as tempe- s i v e displacements i n t h e s o l i d s t a t e , t h e observed
r a t u r e r i s e s ; t h e temperature dependence of S(qo) o s c i l l a t i o n s a r e more pronounced and t h e shoulders
i s i d e n t i c a l f o r these t h r e e metals, as shown i n seen i n 1i q u i d s appear b e t t e r defined.
F i g . 4 where t h e r a t i o o f t h e h e i g h t [ S ( q o ) l T t o
IJe t h i n k t h a t such a s i m i l a r i t y between t h e
that Observed at the point [S(qo)l~m are l i q u i d and t h e amorphous s t r u c t u r e s -supported by
p l o t t e d as a f u n c t i o n o f t h e reduced temperature
t h e f a c t t h a t t h e amorphous f i l m s do c r y s t a l i i z e t o
t h e same v a r i e t i e s t h a t supercooled l i q u i d s - must
be connected w i t h t h e process used t o o b t a i n amor-
phous samples. Indeed, i n p r e p a r i n g Ga and B i f i l m s
[O B i by vapour deposition, atoms ( o r i o n s ) impinge o n t h e
cooled s u b s t r a t e w i t h an i n i t i a l k i n e t i c energy
wnnous 8 H~ s u f f i c i e n t t o d i s t u r b t h e atoms p r e v i o u s l y deposi-
t e d and t o r a i s e temperature l o c a l l y up t o t h e mel-
t i n g p o i n t ; o b v i o u s l y t h i s e f f e c t concerns few
atoms around t h e p o i n t s o f impact and t h e quench
r a t e i s r a p i d enough t o garantee n o n - c r y s t a l l i n e
1L I I I
T I T~
-
s o l i d f o r m a t i o n w i t h some reminiscence o f l i q u i d
0.5 1.0 1.5 s t a t e . Because o f t h e h i g h vapour pressure o f mer-
rlqur. atl lo o f me U r p n r siq,: of :M *frtt oeak of cne I ~ g u l dsmmctum
4
factor 1:mat Wsennt c?os. umr l t l m mtnt in. rlw:d rr a
c u r y i t i s p o s s i b l e t o produce f i l m s w h i l e the eva-
' u n c t m a t tn, reducnt t-raure - / ~ n In. f u l l ltn -n>ch reore-
rents tne c u n e qlv.n ¶y llqnr [ I l l for l a am.? s u i r N s C N n
p o r a t i o n c r u c i b l e i s maintained a t low temperature;
w o l ~ * t *In~ta. rurrcmlca %ram
atoms reach t h e s u b s t r a t e w i t h o u t ~ r o d u c i n at o o<

From S(q) , t h e p a i r c o r r e l a t i o n f u n c t i o n s ,
much damage : t h e s t r u c t u r e f a c t o r o f t h e amorphous
g ( r ) ( F i g . 5, 6 and 7), can be obtained i n t h e f i l m thus obtained ( F i g . 3) e x h i b i t no shoulder on
standard way by F o u r i e r t r a n s f o r m a t i o n : t h e s t r u c -
t h e f i r s t peak and r a t h e r looks l i k e t h e hard sphe-
t u r e o f l i q u i d Ga and Hg remains q u i t e unchanged
r e d e s c r i p t i o n and t h e n o n - c r y s t a l l i n e s o l i d s t r u c -
when t h e temperature i s lowered except some i n c r e a -
t u r e o f mercury ( F i g . 3 and 7) n o t a b l y d i f f e r s f r a n
se i n t h e l a r g e range c o r r e l a t i o n . I t i s o f p a r t i -
t h a t i n the l i q u i d state.
c u l a r i n t e r e s t t o n o t e t h a t e x ~ e r i m e n t s on Ga and
Hg have been performed i n t h e s t r o n g l y supercooled The normalized f i r s t peak h e i g h t o f t h e s t r u c -

state close ti, the ul stability limit of the t u r e f a c t o r obtained from t h e experiments c a r r i e d
l i q u i d s t a t e b u t no s t r i k i n s feature is seen either Out On the three are in
"

i n S(q) o r i n g ( r ) concerning any i n c i p i e n t ordered F i g . 4 : t h e r e i s s t r o n g evidence t h a t t h e p l o t s

s t a t e as suggested by mean f i e l d theory ~h~~ corresponding t o t h e non c r y s t a l l i n e s t a t e do n o t
l i e on t h e curve expected from e x t r a p o l a t i o n o f the
l i q u i d s t a t e ; i t seems probable t h a t t h i s occur- REFERENCES
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