Mat. Res. B u l l . , Vol. 23, p p . 813-819, 1988. P r i n t e d in the USA.

0025-5408/88 $3.00 + .00 C o p y r i g h t (c) 1988 Pergamon P r e s s plc.

PURIFICATION OF LEAD CHLORIDE FOR USE AS HIGH-TEMPERATURE

SOLVENT IN THE GROWTH OF CRYSTALS OF I I - V I COMPOUNDS

J . E c k s t e i n , R.Nitsche, J.Trauth and R.Gutmann

K r i s t a l l o g r a p h i s c h e s I n s t i t u t der U n i v e r s i t ~ t
Hebelstrasse 25 D-7800 Freiburg FRG

( R e c e i v e d F e b r u a r y 23, 1988; Communicated b y A. Rabenau)

ABSTRACT
A process f o r removing oxygen i m p u r i t i e s from PbClz is
described which c o n s i s t s of three steps: C h l o r i n a t i o n
with gaseous SiCl4, high-temperature f i l t r a t i o n of the
molten PbClz and d i r e c t i o n a l s o l i d i f i c a t i o n i n t o l a r g e l y
monocrystalline ingots of defined diameters.

MATERIALS INDEX: c h l o r i d e s , lead

Introduction

Molten mixtures o f PbO and PbF2 are widely-used high-

temperature solvents f o r f l u x growth o f oxide c r y s t a l s ( I ) , but
they are unsuited f o r chalcogenides ( o x i d a t i o n , a t t a c k o f noble
metal c r u c i b l e s ) . Preliminary experiments on the f e a s i b i l i t y of
growing I I - V I compouds from f l u x e s i n d i c a t e d , t h a t n o n - f l u o r i d i c
Pb-halides ( e s p e c i a l l y PbCl2) and t h e i r mixtures with the
corresponding I I - h a l i d e s are e f f e c t i v e chalcogenide solvents ( 2 ) .
Since they can be handled in Quartz vessels, they allow v i s u a l
observation of the d i s s o l u t i o n and c r y s t a l l i z a t i o n processes.
However, attempts t o e m p l o y the t r a v e l l i n g heater method
(THM) met with serious d i f f i c u l t i e s when commercial PbCl2 (Merck
>99%) was used. The s o l i d i f i e d solvent adhered t e n a c i o u s l y t o the
w a l l s of the Quartz ampoules, which o f t e n cracked upon c o o l i n g .
F i g . l a demonstrates the r e s u l t of a model experiment, in which a
PbCl2 melt was d i r e c t i o n a l l y s o l i d i f i e d in a v e r t i c a l two zone
furnace at a rate o f 2mm/h. and then cooled t o room temperature
with 10K/h. The material is hazy, brownish discoloured and s t i c k s
to the ampoule, the l e f t p a r t of which broke o f f . No improvement
was noted with PbClz which had been p r e c i p i t a t e d from a lead
acetate s o l u t i o n , using a n a l y t i c a l grade reagents.
In g r a p h i t i z e d ampoules, partial destruction of the
p r o t e c t i v e coating was noted.
813
814 J . E C K S T E I N , et al. Vol. 23, No. 6

FIG. I
D i r e c t i o n a l l y s o l i d i f i e d PbCl= ingots
Top (a): Without any treatment
Bottom (b): After SiCl4 treatment

The conclusion was, that PbCl= contained oxidic impurities,

which had to be removed p r i o r to crystal growth.
Oxygen is l i k e l y to be present in PbCl2, since i t is usually
prepared f r o m aqueous solutions. In addition to OH" groups,
replacing Cl" by p a r t i a l hydrolysis, the presence of 0 - - , oxides
and o x i d e - c h l o r i d e s i s t o be e x p e c t e d .
At f i r s t i t was t r i e d t o remove o x i d i c i m p u r i t i e s by repeated
vacuum d i s t i l l a t i o n of molten PbClz The o b t a i n e d m a t e r i a l was
greyish discolored; it still "reacted" w i t h q u a r t z and g r a p h i t e .
Microscopic examination revealed tiny, black particles, probably
Pb, r e s u l t i n g from c h l o r i n e l o s s e s , as has been s t a t e d i n ( 3 ) .
In the l i t e r a t u r e , oxygen removal by c h l o r i n a t i o n w i t h CI=
and HCI has been suggested ( 4 ) . W i l l e m s e n ( 5 ) proposed c h l o r i n a t i o n
with CC14, and subsequent zone m e l t i n g . However, he r e p o r t s a l s o
the formation of carbon p a r t i c l e s in t h i s p r o c e s s , which are o n l y
u n c o m p l e t e l y swept away by the s o l i d i f i c a t i o n front.
Since it is known t h a t OH" i m p u r i t i e s in a l k a l i h a l i d e s can
be e f f e c t i v e l y removed with SIC14 (6), we attempted to apply t h i s
agent also to PbCl=.
This paper describes a p u r i f i c a t i o n procedure, consisting
e s s e n t i a l l y of three steps:
(a) Chlorination of PbClz with gaseous SiCl4
(b) Removal of the reaction products (SiOz, lead s i l i c a t e s ) by
high-temperature f i l t r a t i o n of molten PbCl=
(c) Segregation of remaining soluble impurities by directional
freezing of the melt.
 Vol. 23, No. 6 LEAD CHLORIDE 815

The p u r i f i c a t i o n apparatus

Fig.2 is a schematic drawing o f the apparatus developed. I t s

central p a r t is the p u r i f i c a t i o n tube P, s i t u a t e d in a t r a n s p a r e n t
furnace, c o n s i s t i n g o f a Kanthal-wired quartz tube Q (l=450mm;
d=3Omm), an i n s u l a t i n g glass tube G (d=9Omm) and two ceramic
endplates E. The tube P is divided i n t o an upper compartment UC
(l=230mm; d=28mm), in which PbCl2 can be t r e a t e d with SiCl4 vapour
and a lower compartment LC (l=190mm; d=15mm),into which the
c h l o r i n a t e d melt is f i l t e r e d v i a the f r i t t e d disk D (pore width:
15-40Nm) and then d i r e c t i o n a l l y s o l i d i f i e d . The pointed end o f LC
serves as s e e d s e l e c t o r to promote s i n g l e c r y s t a l l i n e growth. The
inlet of P is connected (by a nylon f l a n g e N, f i t t e d with a Viton
gasket) t o a t r a i n of valves VI-V4. They permit the p u r i f i c a t i o n
tube to be a l t e r n a t i v e l y evacuated, flushed with argon or f i l l e d
with SiCl4. The SiCl4 concentration is determined by the
temperature (vapour pressure at 298K: 231Torr) o f the storage
vessel SV. The b a l l - j o i n t s BI-B3 provide f l e x i b i l i t y and allow
rapid disassembling f o r cleaning. The whole apparatus is grease-
f r e e , a l l connections and movable parts are t e f l o n - l i n e d .

Vl V2 v3 V4

FIG.2
B1 ~ svB2

pbc2'cuc
(a) P u r i f i c a t i o n apparatus
(Not t o scale) SiCI4 VIllA
i
11 .r//,~" E
See text for symbols ~j ,,

~
(b) PbClz melt a f t e r SiCl4
treatment
(c) PbCl2 melt a f t e r high-
temperature f i l t r a t i o n R

C g D I
LC
el | J a
ii D i
' V i'b--O
(a ) P'/////////..~ E
(b

P u r i f i c a t i o n procedure

C h l o r i n a t i o n with SiCl4

A f t e r closing Vl and V2, P is evacuated with a r o t a t i o n pump

to 10-2 Torr. In the meanwhile, the furnace is heated to 523K. By
c l o s i n g V4 and opening V2, the PbCl2 bar in UC (50gr; compacted in
 816 J. ECKSTEIN, e t al. Vol. 23, No. 6

a nylon p r e s s ) i s exposed to SIC14 vapours f o r about 5min. These

evacuation and c h l o r i n a t i o n cycles are repeated three times. A f t e r
the l a s t admission o f SiCl4, the furnace temperature i s raised to
melt the PbClz (MP: 7 7 4 K ) . The s i t u a t i o n shown in f i g . 2 b a r i s e s .
White and dark p a r t i c l e s can be seen f l o a t i n g in the melt M. Note
i t s n o w convex meniscus, in c o n t r a s t t o the concave menisci
(strong w e t t i n g ) of non-chlorinated melts.

Hi,h-temperature f i l t r a t i o n of PbCIz

The melt i s now pressed through the f r i t t e d f i l t e r disk D

w i t h SiCl4-saturated argon (650Torr), admitted v i a VI, V2, V3. The
filtered PbCl2 i s transparent and s l i g h t l y y e l l o w i s h , i t s meniscus
remains convex. The r e a c t i o n products R, m i x e d with a PbCl2
residue, remain on D ( f i g . 2 c ) .
The melt i s cooled under SiCl4 to room temperature. The
r e s u l t i n g ingot i s p o l y c r y s t a l l i n e and contains many hollows. Then
the furnace i s removed, LC i s evacuated through D t o 10-STorr,
drawn-off a t the c o n s t r i c t i o n C and f i t t e d with a holding rod.

Further p u r i f i c a t i o n by d i r e c t i o n a l s o l i d i f i c a t i o n

The PbClz ingot i s now remelted in the upper section (T=840K)

of a transparent, v e r t i c a l two-zone furnace and kept s t a t i o n a r y
for 24hrs. This proved to be advantageous to allow sedimentation
of w h i t i s h p a r t i c l e s i n t o the t i p of the ampoule. Apparently, they
o r i g i n a t e d from t i n y seeds, which had passed the pores o f the
filter, by Ostwald r i p e n i n g . I t i s assumed t h a t these p a r t i c l e s
are PbSi03, the only phase in the system having a higher d e n s i t y
(DzgaK=6.49g/CC) than molten PbCl2 (D823K=4.93g/CC).
Directional freezing is i n i t i a t e d by lowering the ampoule at
a r a t e of 2mm/hr i n t o the colder section (T=650K) of the furnace.
It i s i n t e r e s t i n g to note t h a t c h l o r i n a t e d PbCl2 melts can be
s t r o n g l y (70-I00K) undercooled, another i n d i c a t i o n o f high p u r i t y .
The r e s u l t i n g spontaneous c r y s t a l l i z a t i o n o f a large p a r t o f the
fluid prevents c o n t r o l l e d s o l i d i f i c a t i o n during the f i r s t run.
Therefore, the ampoule has to be c a r e f u l l y raised again towards
the hot section of the furnace, s u c h t h a t a s m a l l , conical seed
remains in the t i p . Renewed lowering w i l l now r e s u l t in c o n t r o l l e d
solidification. Seed s e l e c t i o n takes place e a s i l y , and in most
cases the l a r g e s t p a r t o f the ingot w i l l be s i n g l e - c r y s t a l l i n e .

Results and discussion

Fig.lb shows a single crystal, made by seeded, directional

solidification of SiCl4-chlorinated PbClz. It is c o l o r l e s s ,
t r a n s p a r e n t , shows no cracks and s l i d e s f r e e l y in the ampoule. No
p h o t o l y t i c d i s c o l o r a t i o n was noted a f t e r one y e a r ' s exposure to
d a y l i g h t . In c o n t r a s t , ingots made from commercial and from
distilled material turned brownish-black a f t e r I - 3 weeks. This
d i s c o l o r a t i o n has been ascribed to c o l l o i d a l Pb ( 7 ) . The o p t i c a l
transmission of a polished disk of 9.4mm thickness was measured.
It s t a r t s to r i s e a t 300 pm and reaches a value o f 70% a t 1000 Nm.
The sample remained h i g h l y transparent (78%) up t o 16~m, where the
 Vol. 23, No. 6 LEAD CHLORIDE 817

steep long-wavelength absorption e d g e s t a r t s . This is in good

agreement with the transmission curves o f Moss and Peacock (8).
High purity is also indicated by the absence o f s p e c i f i c
absorption bands in the whole transmission range, contrary e.g. to
r e s u l t s of Singh e t al (9) on PbBr2.
Preliminary experiments proved t h a t the material i s suited
for use as f l u x t o grow I I - V I - c r y s t a l s such as ZnSe, CdS, CdTe. I t
is i n e r t against s i l i c a glass and g r a p h i t e f i l m s . The method has
the a d d i t i o n a l advantage t h a t from these "casted" PbCl2 ingots,
c y l i n d e r s can be cut which f i t e x a c t l y the c r y s t a l l i z a t i o n tubes,
used in the subsequent THM process.
Although the p r a c t i c a l success of the p u r i f i c a t i o n method is
evident, i t was not possible to obtain a q u a n t i t a t i v e p i c t u r e of
the nature of the i m p u r i t i e s and the degree of their removal,
because of lack of proper a n a l y t i c a l facilities. A direct
i d e n t i f i c a t i o n of the reaction products, c o l l e c t e d on D, by
diffraction methods also f a i l e d . The amounts were too small and
they seemed to occur in amorphous or glassy s t a t e s . The f o l l o w i n g
discussion is therefore mainly based on i n d i r e c t evidence,
thermodynamic arguments and l i t e r a t u r e data.
In the s t a r t i n g m a t e r i a l , the f o l l o w i n g elements h a v e been
detected:
- By atomic absorption spectrometry: Cu=0.2; Co=0.2; Ni=0.2;
Mn=O.3; Fe=1.6 and Si=2.5ppm.
- By x-ray fluorescence: non q u a n t i f i a b l e traces of Ca, Zn, Al, Mg
S and P.
In the p u r i f i e d m a t e r i a l , no s i g n i f i c a n t concentration changes
were noted, except an increase of Si t o maximal values of 50ppm.
This indicates that non-metallic impurities, e s p e c i a l l y oxygen,
c o n s t i t u t e the major problem.
In PbClz, oxygen can be conceived t o be present as:
A. Chemisorbed H20. In the l i t e r a t u r e , a value of .03 weight% has
been reported (5). By t i t r a t i o n with K . F i s c h e r ' s reagent, we found
.15% in commercial PbCl2. Water cannot be removed e n t i r e l y by
drying at elevated temperatures. Already well-below the melting
point, h y d r o l y s i s and o x i d a t i o n reactions take place. F i r s t , the
compound Pb(OH)Cl is formed, which e v e n t u a l l y decomposes i n t o PbO
(see below). The r e a c t i o n of H20 with SiCl4 (all following
thermodynamic data are taken from (10)) i s :

(1) SIC14 + 2H20 = Si02 + 4HCI Z~GsooK = -48 Kcal/mole

(B) Hydroxyl ions OH-. They originate from partial hydrolysis

during synthesis and from moisture. Small amounts can be thought
to substitute C1- ions in the PbCl2 lattice, but also formation of
Pb(OH)Cl, which has a similar structure (11) as PbCl2, has to be
considered. However, it is known (12) that this compound
decomposes already between 470 and 520K according to:

(2) 2Pb(OH)CI = PbO + P b C I 2 + H20

Thus, PbO is the final decomposition product of any hydroxyl ions

present in PbClz.
(C) Oxide ions 0--. Such ions can be thought to be present on CI-
sites (charge compensation by CI- vacancies or by trivalent
cations) or in foreign phases, such as PbO or one of the three
lead oxide chlorides known to exist in the PbO-PbCI2 system
(13,14). These phases, form already below the melting point of
 818 J . R C K S T E I N , et al. Vol. 23, No. 6

PbCl2 by decomposition of Pb(OH)CI (according to eQ.2) or by

d i r e c t reaction of PbCl2 with oxygen ( 3 ) . In our case, the oxide
c h l o r i d e with the s m a l l e s t oxygen content, PbO-PbClz, i s the most
probable one. Model reactions f o r the removal of 0-- by SiCl4 are:

(3) SiCl4 + 2PbO = SiOz + 2PbCl2 AGBooK = -101Kcal/mole

(4) SIC14 + 3PbO = PbSiOs + 2PbCl2 AGsooK = -107 Kcal/mole

The high negative f r e e enthalpy values in eas.1, 3 and 4 near

the melting p o i n t of PbClz make these oxygen e x t r a c t i o n reactions
h i g h l y probable.
The p r e c i p i t a t e which formed in the PbC12 melt was r a t h e r
voluminous but of l i t t l e weight (20mg from a 50g PbClz charge). I t
consisted largely of whitish and a few blackish particles. The
latter disappeared u p o n h e a t i n g a b o v e 770K i n a i r and a r e b e l i e v e d
to be c a r b o n . However, it c a n n o t be excluded that some o f them
consist of SiO, w h i c h h a s been o b s e r v e d i n t h e SIC14 t r e a t m e n t of
alkali halides (6). The w h i t i s h residue, even after firing at
IO00K did not yield x-ray patterns. The product is partially
soluble i n HNOs, the residue dissolves in HF. I t is therefore
believed to consist of a mixture of PbSiOs and SiO2, which is
known t o f o r m g l a s s e s .
Finally, it should be p o i n t e d o u t , t h a t a l s o CC14 was t r i e d
as c h l o r i n a t i o n agent for PbClz, according to:

(5) CC14 + 2PbO = CO= + 2PbC12 AGe0oK = -148 Kcal/mole

Despite the favourable f r e e enthalpy, the p u r i f i c a t i o n i s less

e f f e c t i v e : the melts h a v e less pronounced convex menisci and the
ingots are s l i g h t l y discolored. Another p o t e n t i a l , gaseous
c h l o r i n a t i n g agent might be carbonyl c h l o r i d e , which proved to be
effective with a l k a l i h a l i d e s (15), but whose t o x i c i t y is
problematic:

(6) COClz + PbO = COz + PbC12 AGs0oK = -77 Kcal/mole

Summary: C h l o r i n a t i o n with SiCl4 i s an e f f e c t i v e way to remove

oxygen i m p u r i t i e s from PbCl2. I t y i e l d s a product not reacting
with glass or Quartz and s u i t a b l e as f l u x f o r the growth o f I I - V I
c r y s t a l s . ( " P u r i t y i s more than a chain of n i n e s " ) .

Acknowledgements

Thanks are due to B . K r Q t z f e l d t f o r AAS analyses, to B.Donner f o r

glass-blowing and to H . S c h l a t t e r e r f o r mechanical work. Financial
support by the M i n i s t e r o f Research and Technology, Federal
Republic o f Germany, i s g r a t e f u l l y acknowledged.
 ii

Vol. 23, No. 6 LEAD CHLORIDE 819

References

I. O.Elwell and H.J.Scheel, Crystal Growth from High-Temperature

Solutions, Academic Press~ London (1975)

2. M.Bruder, PhD-Thesis, Freiburg (1986)

3. A.Kaldor and G.A.Samorjai, J.Phys. Chem.70, 3538 (1966)

4. Ja.I.Ivashentsev, V.I.Ivantsova and A.N.Ketov, Russ.J.Inorg.

Chem. 12, 455 (1967)

5. B.Willemsen, J.Solid State Chem.~, 567 (1971)

6. J.Eckstein, V.Gross and E.Rubinova, K r i s t a l l & Technik3,

583 (1968)

7. J.F.Verwey, J . P h y s . Chem. S o l i d s 27, 468 (1965)

8. T.S.Moss and A.G.Peacock, Infrared Physo~, 104 (1961)

9. N.B.Singh, M.Gottlieb, J.J.Conroy, R.H.Hopkins and R.Mazelsky,

J . C r y s t a l Growth 87, 113 (1988)

10. I . B a r i n , O.Knacke and O.Kubaschewski, Thermochemical P r o p e r -

t i e s of Inorganic Substances (Suppl.), Springer Verlag,
Berlin (1977)

11. S.Goldsztaub, C.R.Acad.Sci.208, 1234 (1939)

12. P.Ramamurthy,E.A.Sicco and M.Badri, Can.J.Chem.48, 2617 (1970)

13. R.Ruer, Z.Anorg.Allgem. Chem.49, 365 (1906)

14. A.Baroni, A t t i Reale Acad. Lincei 20, 384 (1934)

15. M.Lebl and J.Trnka, Z.Physik 1.86, 128 (1965)