ACS Symposium Series - ACS Publications - American Chemical

Chapter 15 S t r u c t u r e - P r o p e r t y Relationships for RBa Cu O Phases 2

1

3

x

1

1

1

1

C. C. Torardi , E. M. McCarron , M. A. Subramanian , H. S. Horowitz , J. B. Michel , Arthur W. Sleight , and D. E. Cox 1

2

1

Central Research and Development Department, Ε. I. du Pont de Nemours and Company, Experimental Station, Wilmington, DE 19898 Physics Department, Brookhaven National Laboratory, Upton, NY 11973 2

Downloaded by UNIV OF AUCKLAND on May 3, 2015 | http://pubs.acs.org Publication Date: August 28, 1987 | doi: 10.1021/bk-1987-0351.ch015

The structures of several 1-2-3 compounds, e.g. YBa Cu O , have been refined from powder neutron diffraction data collected at 298 K. Orthorhombic symmetry was found for the superconducting phases NdBa Cu O , YBa Cu 0 , and ErBa Cu O . The short Cu-O distance of about 1.85Å decreases with increasing size of the rare earth cation, but the average Cu-O distance in the chains remains nearly constant. Refinement of a reduced YBa Cu O phase shows that a tetragonal YBa Cu O composition can be achieved before structural collapse. This phase is semiconducting and not superconducting. We have also prepared a sample of YBa Cu O with the tetragonal 1-2-3 structure where oxygens have not ordered in a way to produce the linear (-Cu-O-) chains. This form of YBa Cu O is not superconducting above 4.2 K. The structure of La Ba Cu O with the tetragonal 1-2-3 structure was refined and again there are no linear (-Cu-O-) chains and no superconductivity. On the basis of these six structural refinements, we tentatively conclude that the (-Cu-O-) chains are required for superconductivity. 2

2

3

2

3

7

6.85

3

2

3

6.91

6.99

2

3

7-x

2

3

6

2

3

7

n

2

1.5

1.5

3

3

7

7.33

n

n

Ever since the identification of the 1-2-3 compound ( i . e . RBa Cu 0 where R = Y or nearly any lanthanide) as a high 2

3

x

0097-6156/87/0351 -0152$06.00/0 © 1987 American Chemical Society

In Chemistry of High-Temperature Superconductors; Nelson, D., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 1987.

15.

TORARDI ET AL.

Structure-Property

153

Relationships

temperature s u p e r c o n d u c t o r , c o n s i d e r a b l e e f f o r t has been e x p e n d e d t o u n d e r s t a n d t h e r e l a t i o n s h i p between t h e s u p e r c o n d u c t i v i t y and t h e s t r u c t u r a l f e a t u r e s o f t h e s e compounds. A l t h o u g h t h e s e compounds a r e s t r u c t u r a l l y r e l a t e d t o t h e i d e a l AM0 p e r o v s k i t e s t r u c t u r e , t h e r e a r e e x t e n s i v e o x y g e n v a c a n c i e s and t h e r e a r e two d i s t i n c t A cation sites. F u r t h e r m o r e , compounds w i t h t h e b a s i c 1-2-3 s t r u c t u r e may have e i t h e r t e t r a g o n a l o r o r t h o r h o m b i c symmetry d e p e n d i n g on t h e o x y g e n v a c a n c y ordering. We have u s e d t h e h i g h r e s o l u t i o n G u i n i e r x - r a y powder d i f f r a c t i o n t e c h n i q u e t o d e t e r m i n e w h e t h e r a g i v e n compound i s t e t r a g o n a l o r o r t h o r h o m b i c . Powder n e u t r o n d i f f r a c t i o n d a t a have b e e n o b t a i n e d f o r r e f i n e m e n t b y t h e Rietveld p r o f i l e technique. Since c r y s t a l s of o r t h o r h o m b i c 1-2-3 compounds seem t o be i n v a r i a b l y twinned, t h e r e i s l i t t l e advantage t o s i n g l e c r y s t a l techniques. Furthermore, the g r e a t e r r e l a t i v e s c a t t e r i n g power o f o x y g e n w i t h n e u t r o n s compared t o x - r a y s a l l o w s f o r d e t e r m i n a t i o n o f t h e o x y g e n c o n t e n t e v e n when i m p u r i t y phases a r e p r e s e n t . We h a v e u s e d n e u t r o n d i f f r a c t i o n t o e l u c i d a t e t h e s t r u c t u r e o f v a r i o u s 1-2-3 compounds a s a f u n c t i o n o f R c a t i o n t y p e a n d r a t i o o f R t o Ba. We have a l s o r e f i n e d v a r i o u s t e t r a g o n a l and o r t h o r h o m b i c s t r u c t u r e s as a f u n c t i o n o f oxygen c o n t e n t . One o b j e c t i v e was t o d e t e r m i n e t h e range o f oxygen c o n t e n t o v e r which t h e 1-2-3 s t r u c t u r e c a n e x i s t . Of p a r t i c u l a r i n t e r e s t was the q u e s t i o n o f whether o r not s u p e r c o n d u c t i v i t y e x i s t s i f t h e l i n e a r -(Cu-Of c h a i n s , a prominent s t r u c t u r a l f e a t u r e of the orthorhombic Y B a C u 0 s t r u c t u r e , are disrupted.


3

n

2

3

7

Synthesis Most o f t h e 1-2-3 compounds were p r e p a r e d f r o m a p p r o p r i a t e r a t i o s o f r e a g e n t g r a d e CuO, B a C 0 , L a 0 , Nd 0 , E r 0 and/or Y 0 . The r a r e e a r t h o x i d e s were f i r e d a t 1000°C b e f o r e weighing. After grinding together i n a m o r t a r , t h e i n t i m a t e m i x t u r e was h e a t e d i n a i r t o 9 5 0 ° C and h e l d f o r a t l e a s t 24 h o u r s . T h i s was f o l l o w e d by c o o l i n g i n a i r t o room t e m p e r a t u r e a t a b o u t 1 5 0 ° / h o u r . One s a m p l e o f Y B a C u 0 was p r e p a r e d b y an o x a l a t e precursor technique. Appropriate q u a n t i t i e s of reagent grade n i t r a t e s o f Y , B a and C u were d i s s o l v e d i n w a t e r and a d d e d d r o p w i s e t o 1M o x a l i c a c i d u s i n g a b o u t 50% e x c e s s o v e r t h a t r e q u i r e d t o c o n v e r t a l l m e t a l s t o oxalates. The r e s u l t i n g b l u e s l u r r y was s p r a y d r i e d i n a B u c h i No. 190 m i n i s p r a y d r y e r o p e r a t e d w i t h N as the a t o m i z i n g g a s . The i n l e t t e m p e r a t u r e was 2 3 0 ° , a n d t h e o u t l e t t e m p e r a t u r e was 1 0 5 ° C . The chamber a t m o s p h e r e was air. The r e s u l t i n g f i n e b l u e powder was h e a t e d i n a i r a t 8 0 0 ° C f o r a b o u t 20 h o u r s . The sample was t h e n c o o l e d t o room t e m p e r a t u r e a t a c o o l i n g r a t e o f a b o u t 1 5 0 ° / h o u r . 3

2

3

2

3

2

2

3 +

2

3

3

2 +

x

2 +

2


3

154

CHEMISTRY OF HIGH-TEMPERATURE SUPERCONDUCTORS

N e u t r o n Powder

N e u t r o n d i f f r a c t i o n d a t a were c o l l e c t e d a t t h e B r o o k h a v e n N a t i o n a l L a b o r a t o r y H i g h - F l u x Beam R e a c t o r . For these e x p e r i m e n t s , p r e s s e d and s i n t e r e d s a m p l e s o f powder (~10-15g) i n t h e s h a p e o f a c y l i n d e r a p p r o x i m a t e l y 0.9-1.3 cm i n d i a m e t e r and 3.0-3.5 cm i n h e i g h t were used. F u l l s e t s o f d a t a were c o l l e c t e d a t a m b i e n t t e m p e r a t u r e a t 0.1° s t e p - s c a n i n t e r v a l s o v e r a 2Θ r a n g e of 5 to 140°. The e x p e r i m e n t a l c o n f i g u r a t i o n c o n s i s t e d o f a p y r o l y t i c g r a p h i t e monochromator and a n a l y z e r i n t h e (002) and (004) s e t t i n g s , r e s p e c t i v e l y . C o l l i m a t i o n was s e t a t 2 0 , 4 0 , 40 and 20', r e s p e c t i v e l y , f o r t h e i n - p i l e , monochromator-sample, s a m p l e - a n a l y z e r , and analyzer-detector locations. The n e u t r o n w a v e l e n g t h was 2.3695 Â, and h i g h e r o r d e r components were s u p p r e s s e d with a graphite f i l t e r . 1


Diffraction

1

f

Non-superconducting

Tetragonal

Compounds

C o n s i s t e n t w i t h G u i n i e r x - r a y powder p h o t o g r a p h s , the neutron d i f f r a c t i o n patterns f o r Y B a C u 0 , Y B a C u 0 p r e p a r e d a t 8 0 0 ° C , and La s i. s C u 0 were f o u n d t o h a v e t e t r a g o n a l symmetry. For the l a t t e r sample, a l a r g e r t e t r a g o n a l u n i t c e l l (a>/2) has b e e n r e p o r t e d ( 1 ) . We f o u n d no e v i d e n c e i n t h e x - r a y o r n e u t r o n d a t a t o support t h i s l a r g e r c e l l . The d a t a f o r t h e above compounds were f i t t e d by r e f i n e m e n t o f t h e s t r u c t u r e s i n t h e s p a c e g r o u p P4/mmm (No.123) u s i n g t h e R i e t v e l d p r o f i l e method ( 2 ) . A l l p e r o v s k i t e - l i k e o x y g e n - a t o m p o s i t i o n s were i n i t i a l l y i n c l u d e d . S t a r t i n g a t o m i c p o s i t i o n s were as f o l l o w s : Ba ( s i t e 2h) i , i , z ; Y ( s i t e Id) C u ( l ) ( s i t e l a ) 0,0,0; Cu(2) ( s i t e 2g) 0,0,z; 0 ( 1 ) ( s i t e 2g) 0,0,z; 0 ( 2 ) ( s i t e 4 i ) 0 , l / 2 , z ; 0 ( 3 ) ( s i t e 2 f ) 0,J,0; 0 ( 4 ) ( s i t e l b ) 0 , 0 , B e c a u s e t h e o x y g e n c o n t e n t was n o t a c c u r a t e l y known, t h e s i t e o c c u p a n c i e s f o r t h e 0 atoms were a l s o r e f i n e d a l o n g w i t h t h e p o s i t i o n a l and i s o t r o p i c t h e r m a l p a r a m e t e r s . Only oxygen atoms 0 ( 1 ) and 0 ( 2 ) r e f i n e d t o f u l l o c c u p a n c y f o r t h e t h r e e compounds. A c h e c k on t h e m e t a l atom m u l t i p l i e r s showed t h e s e s i t e s t o be f u l l y o c c u p i e d . The s t o i c h i o m e t r y o b t a i n e d from the p r o f i l e a n a l y s e s a r e g i v e n i n T a b l e s I and I I . The t e t r a g o n a l s a m p l e o f Y B a C u 0 c o n t a i n e d a s m a l l amount o f B a C 0 i m p u r i t y t h a t c o m p l i c a t e d t h e p r o f i l e b a c k g r o u n d c o r r e c t i o n and c o n t r i b u t e d t o t h e i n t e n s i t y o f s e v e r a l peaks thereby r e s u l t i n g i n a r e l a t i v e l y h i g h weighted p r o f i l e R - f a c t o r . From t h e p r e s e n t s t r u c t u r a l r e f i n e m e n t , t h i s compound has b e e n t e n t a t i v e l y f o r m u l a t e d as Y B a C u 0 . A c l e a n sample o f t h i s compound has now b e e n p r e p a r e d and w i l l s o o n be r e e x a m i n e d . In t h e u n i t c e l l o f L a 5 B a C u 0 , t h e r e are^ a v a i l a b l e t h r e e s i t e s f o r t h e l a n t h a n u m and b a r i u m i o n s . B e c a u s e t h e L a / B a r a t i o i s 1:1, two m o d e l s f o r t h e 2

3

6

2

Bdi

1

β

3

2

7 m 3

3

7

3

2

3

7 3 C 1 >

x #

x m 5

3

7


3

7

Structure-Property

TORARDI ET AL.

Table I.

155

Relationships

Atomic P o s i t i o n a l and Thermal Parameters f o r the T e t r a g o n a l (P4/mmm) Compounds Y B a C u 0 , YBa Cu 0 , and L a . B a . C u 0 . > 2

2

3

7 > 3 < 1 >

x

YBa Cu 0


2

3

6

s

1

YBa Cu 0 . 2

3

7

5

3 < 1 >

3

7

3

6

3 3 < 4

La .gBai. Cu 0 . x

5

3

7

3 3 < 4 >

Ba or Ba/La(l)

χ y ζ B(Â2)

0.50 0.50 0.1952(4) 0.9(1)

0.50 0.50 0.1886(9) 1.0(3)

0.50 0.50 0.1814(4) 0.4(1)

Y or La(2)

χ y ζ B(Â2)

0.50 0.50 0.50 0.6(1)

0.50 0.50 0.50 0.4(4)

0.50 0.50 0.50 0.8(2)

Cu(l)

Χ y ζ B(Â2)

0.00 0.00 0.00 1.0(1)

0.00 0.00 0.00 1.9(4)

0.00 0.00 0.00 0.5(2)

Cu(2)

χ y ζ B(Â2)

0.00 0.00 0.3605(3) 0.3(1)

0.00 0.00 0.3559(7) 0.5(2)

0.00 0.00 0.3465(3) 0.3(1)

0(1)

Χ y ζ B(Â2)

0.00 0.00 0.1518(4) 1.5(1)

0.00 0.00 0.1567(9) 1.3(5)

0.00 0.00 0.1562(6) 2.3(3)

0(2)

Χ y ζ B(Â2)

0.00 0.50 0.3794(2) 0.7(1)

0.00 0.50 0.3759(6) 1.3(3)

0.00 0.50 0.3657(3) 1.0(1)

0(3)

χ y ζ Β (£2) atom/site

0.00 0.50 0.00 1.00 0.02(1)

0.00 0.50 0.00 12(2) 0.63(5)

0.00 0.50 0.00 7.1(7) 0.64(1)

0(4)

χ y ζ B(Â2) atom/site

0.00 0.00 0.50 1.50 0.08(3)

0.00 0.00 0.50 1.50 0.08(2)

a(Â) c(Â) R

NUC ί*) Rwp (%) R (%) E

— — — — 3.8519(1) 11.8037(4)

3.8657(3) 11.6015(17)

3.9024(2) 11.6908(9)

3.9 11.5 5.8

7.6 19.1 7.9

2.5 11.0 6.5



T a b l e I I . Bond D i s t a n c e s i n the T e t r a g o n a l (P4/mmm) Compounds YBa Cu 0 , Y B a C u 0 , and L a . Β 3 . C u 0 .


2

3

6

2

YBa Cu 0 2

3

3

6

7 > 3 < 1 >

YBa Cu 0 . 2

Β

x

3

7

3 < 1 >

Λ

5

3

7

La .gBai. Cu 0 . x

5

3

cu(i)-od) Cu(l)-0(3)*

1 .792(5)

1.818(10) 1.933

1.826(7) 1.951

Cu(2)-0(1) Cu(2)-0(2) Cu(2)-0(4)»

2 .463(4) 1 .939(1)

2.311(9) 1.947(2) 1.672(3)

2.225(6) 1.964(1) 1.795(2)

Ba-O(l) Ba-0(2) Ba-0(3)»

1 .772(2) 2 .905(4)

2.758(3) 2.908(9) 2.919(7)

2.775(3) 2.907(6) 2.882(3)

La/Y-0(2) La/Y-0(4)*

2 .395(1)

2.410(3) 2.733

2.504(2) 2.759

a

T h e s e oxygen atom s i t e s

3 3 < 4 >

7

are p a r t i a l l y o c c u p i e d , see T a b l e I.


3 3 < 4 )


15.

Structure-Property

TORARDI ET AL.

157

Relationships

l a r g e - c a t i o n o r d e r i n g were e x a m i n e d . One m o d e l p l a c e d the ions at h a l f occupancy i n a l l three s i t e s . The s e c o n d model p l a c e d a f u l l La a t and t h e r e m a i n i n g lanthanum along w i t h a l l of the barium s t a t i s t i c a l l y d i s t r i b u t e d over the i , i , z s i t e s . I t was e v i d e n t f r o m t h e r e f i n e m e n t t h a t t h e s e c o n d model was b e s t . In f a c t , t h e o c c u p a n c i e s o f t h e L a and Ba i o n s a t i , i , z were r e f i n e d w i t h t h e c o n s t r a i n t t h a t t h e sum o f t h e o c c u p a t i o n f a c t o r s must g i v e a f u l l y o c c u p i e d s i t e . To w i t h i n one-half of a standard d e v i a t i o n u n i t , these s i t e s were f o u n d t o c o n t a i n 75% Ba and 25% L a . During these r e f i n e m e n t s , t h e ζ c o o r d i n a t e s f o r Ba and L a were c o n s t r a i n e d t o be e q u a l as were t h e i s o t r o p i c Β v a l u e s . Atoms 0 ( 1 ) and 0 ( 3 ) e x h i b i t e d r e l a t i v e l y h i g h i s o t r o p i c Β v a l u e s , 2.3(3) and 7.1(7) Â , r e s p e c t i v e l y . T h e y were then r e f i n e d with a n i s o t r o p i c terms. B o t h showed v e r y large B i and B o v a l u e s on t h e o r d e r o f 4 Â f o r 0(1) and 9 pfi f o r 0 ( 3 ) . T h e s e a r e b e l i e v e d t o be an a r t i f a c t due t o t h e s t a t i s t i c a l d i s o r d e r o f b a r i u m and l a n t h a n u m on t h e 0,0,ζ s i t e s . B o t h o x y g e n atoms b o n d t o t h e s e m e t a l i o n s , and f o r any g i v e n M-0 (M = Ba, La) bond, t h e La-0 bond l e n g t h s a r e e x p e c t e d t o be s h o r t e r t h a n t h e Ba-0 d i s t a n c e s ( e . g . , t h e r e s p e c t i v e sums o f t h e i o n i c r a d i i (3) f o r La-0 and Ba-0 a r e 2.67 and 2.92 Â ) . This means t h a t i n some o r a l l o f t h e u n i t c e l l s t h e s e 0 atoms a c t u a l l y a r e l o c a t e d s l i g h t l y away f r o m t h e i r ' i d e a l positions (4). F u r t h e r d e t a i l s on t h e p r o f i l e a n a l y s e s w i l l be p u b l i s h e d i n t h e f u t u r e . T a b l e I compares t h e r e s u l t s o f these refinements. Interatomic d i s t a n c e s i n the t h r e e t e t r a g o n a l m a t e r i a l s are given i n Table I I . 2

X

2

2

1

Superconducting

Orthorhombic

Compounds

R i e t v e l d p r o f i l e r e f i n e m e n t s were done on t h e compounds NdBa Cu 0 , YBa Cu 0 , and E r B a C u 0 w h i c h a l l h a v e o r t h o r h o m b i c symmetry. *The d a t a f o r t h e s e compounds were f i t t e d by r e f i n e m e n t o f t h e s t r u c t u r e s i n t h e s p a c e g r o u p Pmmm (No. 4 7 ) . The l o w e r c r y s t a l l o g r a p h i c symmetry, r e l a t i v e t o t h e t e t r a g o n a l symmetry d e s c r i b e d a b o v e , s p l i t s some o f t h e o x y g e n atom s i t e s i n t o two i n d e p e n d e n t groups. F o l l o w i n g an a n a l o g o u s p r o c e d u r e u s e d i n t h e refinements of the t e t r a g o n a l m a t e r i a l s , a l l p e r o v s k i t e - l i k e o x y g e n atom p o s i t i o n s were initially i n c l u d e d and t h e s i t e o c c u p a n c i e s f o r t h e o x y g e n atoms were a l s o r e f i n e d . The v a r i a b l e ζ c o o r d i n a t e s were t a k e n from the r e c e n t l y d e s c r i b e d s t r u c t u r e s of Y B a C u 0 . Oxygen atoms 0 ( 1 ) , 0 ( 2 ) , and 0 ( 3 ) ( T a b l e I I I ) r e f i n e d t o f u l l o c c u p a n c y f o r t h e t h r e e compounds. The m e t a l atom s i t e s were a l s o f o u n d t o be f u l l y o c c u p i e d . Comparisons of t h e r e f i n e d s t r u c t u r a l p a r a m e t e r s and o f t h e i n t e r a t o m i c d i s t a n c e s a r e g i v e n i n T a b l e s I I I and IV, respectively. The s t o i c h i o m e t r y o b t a i n e d f r o m t h e r e f i n e m e n t s o f t h e s e compounds i s a l s o g i v e n i n t h e Tables. 2

3

6

9

2

3

6 > 9

2

3

7

2

3


7


Table

III.

A t o m i c P o s i t i o n a l and Thermal P a r a m e t e r s f o r t h e S u p e r c o n d u c t i n g O r t h o r h o m b i c (Pmmm) Compounds NdBa Cu 0 .eg , YBa Cu 0 . , and ErBa Cu 0 < >. 2

2

3

3

NdBa Cu 0 . 2

Ba

X

y B(Â2)


Nd,Y or Er

χ y B(Â2)

Cu(l)

X

y B(Â2) Cu(2)

X

y B(Â2) 0(1)

X

y B(Â2) 0(2)

X

y B(Â2) 0(3)

X

y B(Â ) 2

0(4)

X

y B(Â2) atom/site 0(5)

X

y B(Â2) atom/site a(Â)

b(A) c(A) NUC R R

W

RE

P

(%) (%) (%)

2

3

9 1 < 4 >

6

6

3

6

8 5 < 6 >

YBa Cu 0 2

3

6 > 9 1 < 4 >

ErBa Cu 0 . 2

3

6

0.50 0.50 0.1846(5) 0.9(2)

0.50 0.50 0.1847(4) 0.5(1)

0.50 0.50 0.1838(6) 0.3(2)

0.50 0.50 0.50 0.1(1)

0.50 0.50 0.50 0.2(1)

0.50 0.50 0.50 0.0(2)

0.00 0.00 0.00 1.1(2)

0.00 0.00 0.00 0.4(1)

0.00 0.00 0.00 0.2(2)

0.00 0.00 0.3505(4) 0.3(1)

0.00 0.00 0.3556(3) 0.2(1)

0.00 0.00 0.3563(4) 0.0(1)

0.00 0.00 0.1559(6) 1.1(2)

0.00 0.00 0.1586(4) 0.6(2)

0.00 0.00 0.1596(5) 0.4(2)

0.00 0.50 0.3721(7) 0.8(2)

0.00 0.50 0.3784(5) 0.3(1)

0.00 0.50 0.3790(6) -0.1(2)

0.50 0.00 0.3715(6) 0.5(1)

0.50 0.00 0.3782(4) 0.3(1)

0.50 0.00 0.3791(6) 0.4(2)

0.00 0.50 0.00 1.9(7) 0.71(4)

0.00 0.50 0.00 1.6(5) 0.87(3)

0.00 0.50 0.00 1.8(6) 0.89(4)

0.50 0.00 0.00 1.50 0.14(2)

0.50 0.00 0.00 1.50 0.05(1)

0.50 0.00 0.00 1.50 0.10(2)

3.8687(2) 9.9150(2) 11.7477(8)

3.8179(1) 3.8801(2) 11.6655(6)

3.8123(2) 3.8756(2) 11.6576(7)

3.7 12.8 6.9

2.2 11.1 6.1

3.5 13.6 9.9


9 9

15.

Structure-Property

TORARDI ET AL.

Table IV.

159

Relationships

Bond D i s t a n c e s i n the Orthorhombic (Pmmm) Superconducting Compounds, N d B a C u 0 , YBa Cu 0 . > , and E r B a C u 0 . ' 2


2

3

6

9 1 < 4

2

NdBa Cu 0 2

3

6 # 8 5 < 6 >

3

6

3

YBa Cu 0 . 2

3

6m

8

5< 6 >

9 9< 6 >

6

9 1 < 4 >

ErBa Cu 0 . 2

3

6

cu(i)-od) Cu(l)-0(4)a Cu(l)-0(5)a

1.831(7) 1.957 1.934

1.850(5) 1.940 1.909

1.859(7) 1.938 1.906

Cu(2)-0(1) Cu(2)-0(2) Cu(2)-0(3)

2.286(6) 1.974(2) 1.950(2)

2.298(5) 1.958(1) 1.927(1)

2.295(6) 1.955(2) 1.924(2)

Ba-O(l) Ba-0(2) Ba-0(3) Ba-0(4)a Ba-0(5)

2.773(2) 2.931(5) 2.942(5) 2.906(4) 2.921(4)

2.739(1) 2.958(4) 2.976(4) 2.879(3) 2.899(3)

2.733(2) 2.967(5) 2.988(5) 2.868(4) 2.889(4)

Nd/Y/Er-0(2) Nd/Y/Er-0(3)

2.449(4) 2.472(4)

2.378(3) 2.405(3)

2.373(4) 2.398(4)

a

a

T h e s e oxygen atom s i t e s

9 9 < 6 >

are p a r t i a l l y o c c u p i e d , see T a b l e I I I .


160


Structural

Description

The

s t r u c t u r e s of t e t r a g o n a l YBa Cu^0 , Y B a C u 0 , and s^ i.5 3°7.3 * °f o r t h o r h o m b i c N d B a C u 0 , YBa Cu oê and E r B a C u ^ 0 a r e v e r y c l o s e l y r e l a t e d . A l l s i x s t r u c t u r e s c o n t a i n l a y e r s c o n s i s t i n g of a c o p p e r - o x y g e n framework. Each l a y e r i s c o n s t r u c t e d from two c o p p e r - o x y g e n s h e e t s w i t h c o m p o s i t i o n C u 0 obtained by c o r n e r s h a r i n g o f n e a r l y - p l a n a r C u 0 u n i t s . The two s h e e t s a r e c o n n e c t e d by l i n e a r O-Cu-0 g r o u p s s o t h a t t h e c o p p e r atoms w i t h i n t h e s h e e t s , Cu(2) i n F i g u r e 1, a r e f i v e - c o o r d i n a t e d i n a square pyramidal c o n f i g u r a t i o n . Y B a C u 0 , w h i c h c o n t a i n s no more o x y g e n atoms, has t h i s structure. In t h e o r t h o r h o m b i c Y B a C u 0 - t y p e s t r u c t u r e s , a d d i t i o n a l o x y g e n atoms c o n n e c t t h e l i n e a r O-Cu-0 g r o u p s a l o n g t h e b a x i s m a k i n g t h i s c o p p e r atom, C u ( l ) , p l a n a r and f o u r - c o o r d i n a t e d , and c r e a t i n g i n f i n i t e O-Cu-0 s t r i n g s a l o n g t h e b d i r e c t i o n . In t h e t e t r a g o n a l YBa^Cu 0 and L a s ^ ^ i . B C U 0 compounds, t h e a d d i t i o n a l o x y g e n atoms c o n n e c t t h e l i n e a r O-Cu-0 g r o u p s along the a and a t e t r a g o n a l a x e s i n a random f a s h i o n . T h e s e two p h a s e s h a v e v a c a n t a p p r o x i m a t e l y f o r t y percent of the oxygen-atom s i t e s a l o n g the c h a i n s . They a r e a l s o t h e o n l y o n e s t o show a s m a l l amount o f o x y g e n i n t h e Y o r L a l a y e r t h e r e b y f o r m i n g a Cu-O-Cu c o n n e c t i o n b e t w e e n t h e c o p p e r - o x y g e n l a y e r s . The L a - B a m a t e r i a l has a l l o f t h e b a r i u m and o n e - t h i r d o f t h e l a n t h a n u m i o n s s i t u a t e d w i t h i n t h e Cu-0 l a y e r n e t w o r k and t h e r e m a i n i n g l a n t h a n u m i o n s l o c a t e d between t h e l a y e r s . The o t h e r compounds h a v e o n l y Ba w i t h i n t h e c o p p e r - o x y g e n framework and Nd, Y, o r E r between t h e l a y e r s . 2

a

6

2

3

2

2

7 3

a n c

Cu

0

3

< 9 f

2

3

6 m g

7

2

4

2

3

6


2

3

7 > 3

x m

x

3

3

7

7 # 3

2

In t h e r a r e - e a r t h l a y e r , L a , Nd, Y, and E r a r e b o n d e d t o e s s e n t i a l l y e i g h t o x y g e n atoms a r r a n g e d t o f o r m a square p r i s m around the c a t i o n . Barium i s bonded t o e i g h t o x y g e n atoms i n Y B a C u 0 , -10.5 o x y g e n atoms i n t h e t e t r a g o n a l Y and L a - B a compounds, and a l m o s t 10 o x y g e n atoms i n t h e s u p e r c o n d u c t i n g orthorhombic phases. 2

3

6

Discussion T h e r e has b e e n c o n s i d e r a b l e s p e c u l a t i o n a b o u t t h e s i g n i f i c a n c e f o r s u p e r c o n d u c t i v i t y of the l i n e a r -fCu-O^ chains i n the R B a C u 0 compounds. I t s h o u l d be n o t e d that a prominent s t r u c t u r a l f e a t u r e of the o l d T record h o l d e r s , e.g. N b G e , was s t r o n g l y b o n d e d , i n f i n i t e l i n e a r c h a i n s o f Nb. From o u r n e u t r o n d i f f r a c t i o n s t u d i e s , i t a p p e a r s t h a t t h e -fCu-0-)- c h a i n s a r e a n e c e s s a r y requirement f o r s u p e r c o n d u c t i v i t y i n the R B a ^ C u 0 family o f compounds where χ i s a b o u t s e v e n . The e v i d e n c e i s p a r t i c u l a r l y compelling i n the case of orthorhombic v s . tetragonal YBa Cu 0 . The c o m p o s i t i o n and formal o x i d a t i o n s t a t e s f o r c o p p e r a r e e s s e n t i a l l y t h e same, y e t the orthorhombic form w i t h c h a i n s i s s u p e r c o n d u c t i n g with a T o f a b o u t 90 Κ w h e r e a s t h e t e t r a g o n a l f o r m w i t h o u t 2

3

7

c

3

n

3

2

3

x

x

c



15.

TORARDI ET AL.

Structure-Property Relationships

161

(a)

(b)

F i g u r e 1. (a) S t r u c t u r e o f t e t r a g o n a l Y B a C u 0 * , Y B a C u 0 , and L a s i . 5 3 ° 7 . 3 * 0 ( 3 ) and 0 ( 4 ) s i t e s a r e e i t h e r empty o r p a r t i a l l y o c c u p i e d d e p e n d i n g on t h e compound. (b) S t r u c t u r e o f o r t h o r h o m b i c NdBa Cu 0 g, YBa Cu 0 , and E r B a C u 0 . 0 ( 4 ) and 0(5) s i t e s ' a r e p a r t i a l l y o c c u p i e d . 2

B a

2

3

2

7 3

3

6 #

3

C u

x t

2

3

6 > 9

2

3

7


162


c h a i n s i s n o t s u p e r c o n d u c t i n g above 4.2 K. We a l s o s e e t h a t s u p e r c o n d u c t i v i t y d i s a p p e a r s i n the R B a C u 0 series as χ d e c r e a s e s t o w a r d s 6.5 and t h e c h a i n s d i s a p p e a r . A g a i n i n t h e La s i.BCU 0 compound, t h e r e a r e no c h a i n s and no s u p e r c o n d u c t i v i t y above 4.2 K. The C u ( l ) - 0 d i s t a n c e a l o n g t h e l i n e a r c h a i n s i s s i m p l y one h a l f t h e b a x i s . T h u s , t h i s Cu-0 d i s t a n c e i n c r e a s e s m o n o t o n i c a l l y with the i n c r e a s i n g s i z e of the rare earth cation. In v i e w o f t h e a p p a r e n t i m p o r t a n c e o f t h e l i n e a r c h a i n s , i t seems u n e x p e c t e d t h a t T does not c h a n g e s i g n i f i c a n t l y i n a r e g u l a r manner w i t h t h i s c h a n g i n g Cu-0 d i s t a n c e . However, t h e r e i s a c o m p e n s a t i o n effect. As t h e Cu-0 d i s t a n c e a l o n g t h e c h a i n s i n c r e a s e s , t h e s h o r t e r Cu-0 d i s t a n c e s p e r p e n d i c u l a r t o t h i s c h a i n are decreasing. Thus, the average C u ( l ) - 0 d i s t a n c e i n t h e c h a i n s d o e s n o t c h a n g e much i n R B a C u 0 : 1 . 8 9 , 1.89, and 1 . 9 0 Â f o r t h e Nd, Y and E r compounds, r e s p e c t i v e l y . T h e r e f o r e , t h e c o p p e r - o x y g e n framework c a n be v i s u a l i z e d as b e i n g e x p a n d e d i n t h e ab p l a n e and c o m p r e s s e d a l o n g t h e c a x i s as t h e r a r e - e a r t h i o n g e t s l a r g e r . The s i t u a t i o n f o r L a Ba ..yCu 0 compositions with t h e 1-2-3 s t r u c t u r e i s v e r y complex s i n c e t h e r e a r e two c o m p o s i t i o n a l v a r i a b l e s which p l a y a c r i t i c a l r o l e i n whether or not s u p e r c o n d u c t i v i t y i s observed. The v a l u e o f y a p p a r e n t l y n e v e r r e a c h e s z e r o b u t s h o u l d be as low as p o s s i b l e f o r optimum s u p e r c o n d u c t i n g p r o p e r t i e s . The v a l u e o f χ must be c o n t r o l l e d t h r o u g h t h e r m a l treatment and o x y g e n p r e s s u r e . We d e a l o n l y w i t h t h e c a s e o f y = 0.5 i n t h i s p a p e r . T h e r e has b e e n p a r t i a l L a s u b s t i t u t i o n f o r Ba a t t h e Ba s i t e , and t h e v a l u e o f χ i s about 7.3. T h e r e i s more t h a n enough o x y g e n t o f o r m c h a i n s a l o n g one a x i s o n l y . The r e m a i n i n g o x y g e n m i g h t h a v e b e e n d i s o r d e r e d a l o n g one a x i s o n l y , b u t i n s t e a d i t i s d i s o r d e r e d along both axes. T h e r e a r e now no i n f i n i t e •fCu-0)- c h a i n s . I t i s a l s o important to note t h a t the average copper o x i d a t i o n i n L a s i.5 3°7. $ ^ +2.37 w h i c h i s n e a r l y t h e same as i n Y B a C Û 0 , " ι . e . +2.33. A structure for L a s i.5 3 ° 7 . 3 had b e e n p r e v i o u s l y p r o p o s e d on t h e b a s i s o f powder x - r a y d i f f r a c t i o n d a t a ( 1 ) . The p r o p o s e d s t r u c t u r e had t h e same b a s i c c a t i o n p o s i t i o n s as i n t h e 1-2-3 structure, b u t t h e o x y g e n v a c a n c y o r d e r i n g was much d i f f e r e n t . Furthermore, i t was p r o p o s e d t h a t t h e c e l l edge was aV2 d e s p i t e t h e f a c t t h a t t h e r e was a p p a r e n t l y no e v i d e n c e for t h i s larger c e l l . A 1 0 0 r e f l e c t i o n was l i s t e d i n a t a b l e , b u t no o b s e r v e d d v a l u e was g i v e n . Our attempts t o r e f i n e o u r d a t a w i t h t h i s p r o p o s e d s t r u c t u r e met w i t h no s u c c e s s , and we t h u s c o n c l u d e t h a t t h e p r o p o s e d structure (1) i s incorrect. We h a v e now e s t a b l i s h e d t h a t t h e r a n g e o f o x y g e n c o n t e n t i n R B a C u 0 p h a s e s w i t h t h e 1-2-3 s t r u c t u r e i s χ = 6 t o 7. However, i n t h e L a Ba _ Cu 0 system, the v a l u e o f χ c a n c l e a r l y e x c e e d 7. I t appears t h a t the v a l u e o f χ must be r e a s o n a b l y c l o s e t o s e v e n i n o r d e r t o 2

3

X

Ba

1m

3

7

3


c

2

1 + y

2

3

3

7

X

N

Ba

S

Cu

x

2

B

x

2

3

a

C

3

7 m 0

u

m

X

1 + y

2

y

3

X


15.

TORARDI ET AL.

Structure-Property

163

Relationships

have oxygen v a c a n c y o r d e r i n g t o produce t h e o r t h o r h o m b i c structure. T o o much o x y g e n o r t o o l i t t l e o x y g e n c a u s e s a type o f oxygen d i s o r d e r which r e s u l t s i n a t e t r a g o n a l structure. F u r t h e r m o r e , a l t h o u g h R B a C u 0 compounds a r e n o r m a l l y o r t h o r h o m b i c and s u p e r c o n d u c t i n g f o r v a l u e s o f χ c l o s e t o s e v e n , we o b s e r v e s e m i c o n d u c t i n g b e h a v i o r a s χ d e c r e a s e s b e l o w 6.5. Thus f o r Y B a C u 0 , i t seems l o g i c a l t o assume l o c a l i z e d e l e c t r o n b e h a v i o r a n d t o a s s i g n an o x i d a t i o n s t a t e o f +1 t o t h e l i n e a r l y c o o r d i n a t e d c o p p e r a n d an o x i d a t i o n s t a t e o f +2 t o t h e copper i n t h e sheets ( 5 ) . 2

3

x

2

3

6


Literature Cited 1. 2. 3. 4. 5.

Er-Rakho, L.; Michel, C.; Provost, J.; Raveau, B. J. Solid State Chem. 1981, 37, 151. Rietveld, Η. M. J. Appl. Crystallogr. 1965, 2, 65. Shannon, R. D. Acta Crystallogr. 1976, A32, 751. Torardi, C. C.; McCarron, Ε. M.; Subramanian, Μ. Α.; Sleight, A. W.; Cox, D. E., in preparation Torardi, C. C.; McCarron, E . M . ; Bierstedt, P. E.; Sleight, A. W.; Cox, D. E . Solid State Commun., submitted.

RECEIVED

July 6, 1987


ACS Symposium Series - ACS Publications - American Chemical

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