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C R Y S T A L S T R U C T U R E O F T H E Li + C O N D U C T O R
1.956 (1)
1.980 (1) x2
1.982 (1) x2
2.026 (1)
Li(l)--O(2)
Li(l)-O(2')
Li(m)--O(l)
1.80 (2)
2.05 (2) x2
2.15 (2)
Li(2)--0(2)
Li(2)--0(2')
Li(2)--O(1)
1.83 (3)
1.99 (2) x2
2.26 (4)
O(l)--Ti-O(l')
O(l)--Ti-O(2)
O(l)-Ti-O(2')
O(l')-Ti-O(l')
O(l')-Ti-O(2)
O(2)-Ti--O(2')
O(2')-Ti-O(2')
0(2)-Li(1)--0(2')
0(2')-Li(1)-0(2')
O(2)-Li(l)--O(l)
O(2')--Li(l)--O(l)
96.90 (5)
90.70 (5)
80.56 (4)
96.10 (4)
91.87 (5)
80.56 (4)
95.95 (4)
123 (1)
92 (1)
133 (1)
87 (i)
0(2)--Li(2)-0(2')
0(2')-Li(2)--0(2')
0(2)--Li(2)--0(1)
0(2')-Li(2)--0(1)
125 (1)
95 (1)
134 (2)
82 (1)
Li2Ti30 7
The Crystal Structure offl-Si3N4; Structural and Stability Considerations Between ~t- and
fl-Si3N 4
BY REINAR GRON
Ruhr-Universitdt Bochum, Institut ffir Mineralogie, Postfach 2148, D-4630 Bochum, Federal Republic of
Germany
(Received 28 September 1978; accepted 6 December 1978)
Abstract
Introduction
R E I N A R GRC,]N
The synthesis of Si3N 4 by nitriding pure Si at < 1773
K always leads to the a- and fl-phases in varying
proportions.
Wild, Grieveson & Jack (1972) assumed that ctSiaN 4 is an oxonitride, but this has been disproved by
Blegen (1975) and also by structural results (Kohatsu
& McCauley, 1974; Kato, Inoue, Kijima, Yamane &
Kawada, 1975). Therefore it is concluded that fl-Si3N 4
is the stable and a-Si3N 4 a metastable phase of pure
SiaN4.
The crystal structure of fl-SiaN 4 has been described
by Hardie & Jack (1957), Thompson & Pratt (1967)
and Wild et al. (1972). All these determinations were
based on powder photographs. A structure investigation from single-crystal data (Borgen & Seip, 1961)
used only the hk0 reflections, because the centrosymmetric space group P6a/m was assumed.
This paper describes an attempt to clarify the
stability relations between a- and fl-Si3N 4 by Madelung
energy computations. For this it was necessary to have
a structure determination for both phases. A singlecrystal stucture determination for ct-Si3N4 has been
published by Kato et al. (1975); a comparable structure refinement of fl-Si3N 4 is described in the first part
of this paper.
v = 144.98 (5)/~,a
z =2
Spacegroup: P6 a
801
802
Si
N(I)
N(2)
x/a
y/a
Z/C
fill
f22
f33
fl2
fl3
7686 (I)
298 (3)
6667
1744 (1)
3294 (3)
3333
2500
2628 (20)
2392 (55)
23 (1)
27 (3)
29 (3)
23 (1)
26 (3)
29 (3)
88 (8)
102 (20)
126 (40)
12 (1)
11 (2)
15 (2)
--6 (9)
- 3 6 (24)
0
1-728 (2)
1-704 (5)
S i - N ( I ) "l
Si-N(2)
Angle
N - N distance
N(l)"t-Si-N(1) ~
N(I)"-Si-N(2)
N(1)LSi-N(I)"
N(1)LSi-N(2)
N(I)LSi-N(1)"
N(2)--Si-N(1)"
109.4
109.7
113.5
106.7
106.6
110.8
Si~V-N(1)-Si v~
Si~V-N(l)-Si ~
Si~LN(I)-Sff
Si-N(2)-Sff"
125.1 (3)
113.5 (1)
121.3 (3)
119.97 (4)
(2)
(5)
(2)
(1)
(2)
(5)
2.801
2.808
2.902
2.774
2.801
2.878
Angle
Equivalent positions
(i) x + l , y , z
(iii) x - y, - y , z - 0.5
(v) - x , y - x , z - 0 . 5
(vii) - y , y - x, z
1.767 (5)
1.730 (1)
(5)
(9)
(8)
(1)
(5)
(9)
Si-Si distance
3.046
2.902
3.046
2.996
f23
- 1 2 (9)
- 3 7 (21)
0
(1)
(0)
(1)
(1)
(ii) x - y , - y , z + 0 . 5
(iv) - x , y - x, z + 0.5
(vi) x - l , y , z
~Ntll
,tl)
NO)
i
,
r,
NIl)
N~I}
a~,
,'
,().
] --
~'~~.-',- - - . . % ~ ~ ~ . : s i ' ,
REINAR
The relationship between the layers A and B is given
by the following transformation of one atom position
X A from A to an atom position X B in B:
Xn =
X~ +
803
0
with
GRI3N
[ x/a
(1)
,~) = A U c + A U e
o
A
. . . .
pAV-
TAS,
(2)
AUe + p A V .
(3)
(a)
:\
.,
I/
/~'
(b)
Fig. 4. (a) Projection down c of layer A (open circles) and layer B
(full circles) produced by transformation I (see text). The region
enclosed by dotted lines is equivalent to (b) the projection of the
real cvSi3N4 unit cell. (Large circles: N, small circles: Si.)
(a)
(b)
Fig. 3. Projection down a 3 of the ABA sequence (a) produced by
transformation 1 (see text). The region indicated with dotted lines
is equivalent to (b) the projection of the real cvSi3N4 unit cell.
(Large circles: N, small circles: Si.)
(a)
(b)
Fig. 5. (a) The two tetrahedra sequences ofwSi3N 4 along c and (b)
the one tetrahedron sequence offl-Si3N4 along c.
804
THE C R Y S T A L S T R U C T U R E O F fl-Si3N 4
Z2 ~
4roeo
1-
(4)
z 2
rm
--
(5)
47~e0
with
1
rm
s .=
ri
r~ (fit)
M F / r m (A -l)
V t-(]l 3)
tt-Si3N4
66.4505
1- 7430
38-124
73.99
fl-Si3N4
flc-Si3N4
66.5369
66.5156
1.7319
1.7319
38.418
38.404
72.49
72.49
References
1789.
BUSING, W. R., MARTIN, K. O. & LEVY, H. A. (1962).
317-318.
International Tables for X-ray Crystallography (1962). Vol.
III. Birmingham: Kynoch Press.
JOHNSON, C. K. (1965). ORTEP. Report ORNL-3794. Oak
Ridge National Laboratory, Tennessee.
KATO, K., INOUE, Z., KIJIMA, K., YAMANE, T. & KAWADA,