Winder, D. R.

English

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Physics Department 863 80 
+ado S t a t e  Univcirsity c . . .  
. Final  Technical Report 
January 31, 1970 
Including Quarterly Sta tus  Report 
GROWTH OF CRYSTALS OF THE TERNARY SULFIDES 
~ S A  Grant NGR 06-002-074 
A. Introduction 
The object ives  of t h i s  p ro jec t  are :  
1) To e s t ab l i sh  a laboratory f o r  c ry s t a l  growth. 
2) To produce c ry s t a l s  of p rous t i t e  and pyrargyr i te  a s  a t e s t  
of equipment and technique. 
3) To explore add i t iona l  mater ia ls  of l i k e l y  candidacy. 
43' To explore poss ible  means of improving op t i ca l  qual i ty .  
' 5 )  To make a few preliminary evaluations of the  c ry s t a l s .  
It ,was real ized at  the  ou t s e t  t h a t  a l l  these object ives  could not  be 
met dur ing. the  f i r s t  year of operation. The major items f o r  c r y s t a l  
growth furnace, con t ro l le r ,  enclosure - could not  be obtained before t h e  
middle of summer. Thus, the  e f f o r t s  up t o  t h a t  time were of necess i ty  
preliminary and inaccurate  because the  gradients were produced a t  the  
opening of an oversized surplus tube furnace. 
B. Overall  Progress 
The laboratory was es tabl ished i n  Room D-1 of t h e  Engineering - Physics- 
Mathematics Complex of Colorado S t a t e  Universi ty,  Figure 1 shows the  
research furnace., con t ro l le r ,  enclosure and c r y s t a l  saw and Figure 2 is a sketch 
of the  f l oo r  plan of the  toom showing the  general layout of the  f a c i l i t i e s .  The 
x-ray laboratory is across t h e  h a l l  i n  D-15 and consis ts  of a G.E. XRD-5 
d i f f r ac t i on  un i t  with diffractometer,  copper and chromium tubes and cameras - 
https://ntrs.nasa.gov/search.jsp?R=19700018069 2020-03-12T02:11:49+00:00Z
Laue, two Debye-Scherrer, Buerger p reces s ion  and Weissenberg, The Depart- 
ment of Phys ics  h a s  r e c e n t l y  p laced  an o r d e r  t o  f a c i l i t a t e  expanding t h e  
u n i t  t o  a two-tube opera t ion .  This  would make i t  p o s s i b l e  t o  u se  t h e  l i n e  
focus  e x c l u s i v e l y  f o r  t h e  d i f f r a c t o m e t e r  and a l low t h r e e  cameras and t r a c k s  
,i 
t o  be permanently s e t  up on a second t a b l e ,  This modi f ica t ion ,  whi le  n o t  
accounted t o  t h i s  p r o j e c t ,  w i l l  c e r t a i n l y  b e n e f i t  i t  by a l l e v i a t i n g  t h e  
congest ion and minimizing t h e  adjustment-alignment e f f o r t s .  
The l a b o r a t o r y  i s  n e a r l y  completely equipped as planned a yea r  ago. 
Some i t e m s  have s t i l l  n o t  been d e l i v e r e d ,  b u t  a r e  only  now beginning t o  
be needed -- t h e  two c i r c l e  goniometer and manipula tor ,  f o r  example. 
The p r o f i l e  of t h e  furnace  was descr ibed  i n  t h e  second q u a r t e r l y  
r e p o r t  and t h e  curve i s  reproduced h e r e ,  F igu re  3 .  Since  then we have 
taken some a d d i t i o n a l  d a t a  w i t h  coo l ing  water  and s t a i n l e s s  s t e e l  s l e e v e s  
included.  Typica l  p r o f i l e s  a r e  given i n  F igu re  4 .  The e f f e c t  of t h e  
cool ing  c o i l  i s  ev iden t  i n  t h i s  f i g u r e ,  . 
Seve ra l  charges of  p r o u s t i t e  and p y r a r g y r i t e  were prepared us ing  
v a r i o u s  techniques ,  some of our  own inven t ions  as w e l l  a s  those  sugges ted  
by the  l i t e r a t u r e  and pe r sona l  communications. A s  expected we found con- 
tamina t ion  of  t h e  charge by water  was h i g h l y  undes i r ab le ,  Also ou r  a t t e m p t s  
t o  produce a s u c c e s s f u l  charge ( i n  t h e  s e n s e  of q u a l i t y  c r y s t a l  l a t e r )  from 
a mixture of  t h e  s a l t s  Ag2S and As2S3 were n o t  encouraging. The f i n a l  pro- 
cedure f o r  p repa r ing  charges is  t o  u se  t h e  elements  o f  6-nines p u r i t y  and 
r e a c t  at a temperature o f  t h e  o r d e r  of 200 CO above t h e  melt ing p o i n t  o f  
t h e  compound des i r ed .  The v e s s e l s  are cleaned and prepared i n  a s t anda rd  
way, t h e  charge loaded i n ,  t h e  v e s s e l  pumped and hea ted  t o  d r i v e  o f f  any 
/ 
wate r  vapor,  and s e a l e d  under a p a r t i a l  atmosphere of argon, The s e a l e d  
capsule  i s  heated i n  an a u x i l i a r y  furnace i n  a  p r o t e c t i v e  metal  tube. The 
boule i s  inspected  and t h e  growth run i n i t i a t e d .  The run t akes  many hours. 
Of t he  s e v e r a l  runs made, on ly  two have produced c r y s t a l s  of p r o u s t i t e  which 
w e  have f e l t  worthy a£ pre l iminary  examination and expec ta t ion  of f u t u r e  ' 
success .  Figure 5 i l l u s t r a t e s  t h e  v e s s e l  and descr ibes  the  procedure f o r  
preparing a  charge f o r  a  t e r n a r y  system, Ag-As-S i n  p a r t i c u l a r .  
The explora t ion  of o t h e r  m a t e r i a l s  has  n o t  progressed very f a r .  An 
at tempt  t o  grow s u l f u r  c r y s t a l s  by p r e c i p i t a t i o n  from a  CS2 s o l u t i o n  y ie lded  
, I  
a  few smal l  c r y s t a l s  embedded i n  a  p o l y c r y s t a l l i n e  matr ix .  Some of these  
sma l l  c r y s t a l s  a r e  a few mil l ime te r s  on a  s i d e  and show i n t e r e s t i n g  s u r f a c e  
morphology and a  p o l a r i z a t i o n  e x t i n c t i o n ,  This  experiment w i l l  continue 
under va r ious  c o n t r o l l e d  condi t ions .  
C. P l ans  In Current  Ready-State. 
The Ag-As and Ag-Sb s u l f i d e  systems w i l l  be  f u r t h e r  explored wi th  t h e  
immediate goa l  of i n c r e a s i n g  t h e  s i z e  and q u a l i t y  of t h e  c r y s t a l s  produced. 
The sulfur-from-solution run w i l l  be repeated wi th  a t t e n t i o n  t o  temper- 
a t u r e  and growth r a t e  as w e l l  a s  o t h e r  so lven t s .  
G e l  growth i s  a term app l i ed  t o  a  method of c r y s t a l  growth i n  which t h e  
mobi l i ty  of the r e a c t a n t s  is decreased by d i f f u s i o n  through a  ge l .  This  
decreases t h e  growth rate d r a s t i c a l l y  and allows h igh ly  inso lub le  compounds 
t o  grow t o  c r y s t a l s  a£ s e v e r a l  mi l l imeters .  The growth of s u l f u r  w i l l  be 
attempted and a l s o  an i n v e s t i g a t i o n  of t h e  p o s s i b i l i t y  of  growing var ious  
s u l f i d e s  by t h i s  tecfinique . 
D. Future  Plans 
The f u t u r e  p l a n s  f o r  the p r o j e c t  comprise t h e  f u l f i l l i n g  of t h e  objec t -  
i v e s ,  i n  p a r t i c u l a r  fzhe exp lo ra t ion  of o t h e r  s to i ch iomet r i c  compounds i n  
E 
t h e  Ag-As-S and Ag-Sb-S system and t h e  e x p l o r a t i o n  o f  o t h e r  t e r n a r y  s u l f i d e  
systems, such a s  Cu-As-S, Ag-Bi-S, As-Pb-S, Cu-Bi-S. Also bes ides  s u l f u r ,  
one might look  a t  Se-S and Te-S. Going t o  non-sulfur systems, good candida tes  
a r e  I2 and s e v e r a l  i o d i d e s  such as Ge 14, K-Hg-I, Cd 12 ,  T i  13, K-Bi-I .  The 
chalcogenides comprise a l a r g e  fami ly  of  i n t e r e s t i n g  compounds, many of which 
do no t  c r y s t a l l i z e  b u t  i n s t e a d  form g l a s s y  m a t e r i a l s  w i th ,  however, app rec i ab le  
ordering.  I n  t h e  exp lo ra to ry  runs ,  i t  is  a n t i c i p a t e d  t h a t  s e v e r a l  o f  t h e s e  
w i l l  occur  and some may be of i n t e r e s t  t o  t h i s  p r o j e c t .  
$1 
E. Personnel  
Besides t h e  p r i n c i p a l  i n v e s t i g a t o r ,  a graduate  s t u d e n t ,  John Kit terman,  
has  con t r ibu ted  t o  t h e  p r o j e c t ,  handl ing  most of  t h e  r o u t i n e  d e t a i l s  of t h e  
ope ra t ion  of t h e  l a b o r a t o r y  and coopera t ing  d i r e c t l y  w i th  t h e  p r i n c i p a l  in -  
v e s t i g a t o r  i n  t h e  handl ing  of t h e  m a t e r i a l s  and charge p repa ra t ion .  Mainten- 
ance of  t he  l a b o r a t o r y  and c o n t r o l  of  t h e  growth runs  was handled by Kitterman 
and a s e n i o r  E r i c  Rogers. 
Rogers l e f t  f o r  g radua te  school  i n  t h e  F a l l  and Kitterman l e f t  a t  t h e  
end of  January upon completion of t h e  exper imenta l  work f o r  h i s  Ph.D. t h e s i s .  
Another s e n i o r ,  Jon  Gustafson,  con t r ibu ted  t o  t h e  p r o j e c t  dur ing  t h e  summer, 
and a sophomore, Dan Marvel, helped dur ing  t h e  F a l l .  4 
P r i n c i p a l  I n v e s t i g a t o r  
D i s t r ibu t ion :  
5 copies  
2 copies  
Na t iona l  Aeromautics & Space Adminis t ra t ion  
O f f i c e  of  S c i e n t i f i c  & Technical  Informat ion  (Code US) 
Washington, D.C.' 20546 
Na t iona l  Aeronaut ics  & Space Adminis t ra t ion  
E l e c t r o n i c s  Research Center 
575 Technology Square 
Cambridge, Massachuset ts  02139 
B.G. Henr ie  
Con t r ac t s  and Grants  

C, 5 u, L A 13' o/V 47diT y .fd& C G* A' ~2 Ti/' 
- 
Figure 2 


1, Match, clean, d ry  tube ,  cup charges,  
2.  Load Ag, A s ,  S charges.  
3 .  Heat whole tube  t o  150' C and pump, 20 minutes.  Cool. 
(- 
' -- 4 .  Seal  r i n g  - keep A s  charge cool  ( zone 2 a t  < 100° C ) 
5 .  Heat zone 2 t o  - 320' C ,  cool  zone 1 and zone 3 t o  
< 100' C ,  30 minutes u n t i l  d i s t i l l a t i o n  of  As20g i s  
completed i n t o  zone 1. 
6. Heat zone 2 t o  600' C ,  zone 3 t o  ' 200' C ,  cool  zone 1 
<100° C ,  20 minutes u n t i l  d i s t i l l a t i o n  of A s  i n t o  zone 
3 i s  completed. Cool. 
8. React i n  p ro t ec t ed  r e a c t i o n  furnace .  Cool. 
1 
9. In spec t .  
-- --- - - - - - 
, 
' Figure 5 
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L - 
e i -. 


Growth of crystals of the ternary sulfides Final technical report

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