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Crystal Diffraction 14
Crystal Diffraction 14
Crystal Diffraction 14
2 scos
2 (in radians) +
R
R
s: sample height displacement
R: diffractometer radius
s
Length of
a larger error for low angle
scos
peaks for the most accurate
unit cell parameters it is
generally better to use the high
angle peaks for this calculation.
Example for sample height displacement
Assume a crystal; cubic structure; a = 0.6 nm.
Consider the error that can be introduced if the sample
was displaced by 100 microns (0.1 mm) for (100) and
(400) diffraction peaks? Assume = 0.154 nm and R =
225 mm.
2d100 ( 0.6) sin 0.154 7.37
2d 400 ( 0.15) sin 0.154 30.87
a
2d hkl sin d hkl
h2 k 2 l 2
a sin 2 2 Constant for a
2 sin 2 2 given crystal
h k l
2 2 2 h k l 2 2
4a
Define s h2 k 2 l 2
Values for h2 + k2 + l2 for cubic system
SC BCC FCC Diamond S
100 X X X 1
110 X X 2
111 X 3
200 X 4
210 X X X 5
211 X X 6
220 8
221 X X X 9
300 X X X 9
310 X X 10
311 X 11
222 X 12
320 X X X 13
SC: 1, 2, 3, 4, 5, 6, 8, FCC: 3, 4, 8, 11, 12, 16, 19, 20,
BCC: 2, 4, 6, 8, 10, 12, 14, .. Diamond: 3, 8, 11, 16, 19,
SC: 1, 2, 3, 4, 5, 6, 8, s is doubled in BCC,
BCC: 2, 4, 6, 8, 10, 12, 14, .. No s = 7 in SC
Indexing Tetragonal system
1 h2 k 2 l 2
2
2
2 sin / 2d hkl
d hkl a c
2
2
h 2
k 2
l 2
sin
2
2
2
A( h 2
k 2
) Cl 2
hkl
2 d 4 a c
A 2 / 4a 2 ; C 2 / 4c 2
2 h 2 hk k 2 2 l 2
sin 2 A( h 2
hk k 2
) Cl 2
3 a2 4 c 2
A 2 / 3a 2 ; C 2 / 4c 2
4 a b c
More difficult!
Consider any two lines having indices hk0 and hkl
Cl2 put it back get A and B.
guess right (consistent)
not right, try another guesses C
http://www.ccp14.ac.uk/solution/indexing/index.html
Determination of the number of atoms in a unit cell
Indexing the power pattern
shape and size of unit cell (volume)
number of atoms in that unit cell.
in 3
g V in g/cm3
nM VC (1083 cm 3 ) ( 3 ) N 0 (6.022 1023 ) C
cm 1.66054
Determination of Atom positions
1 cos2 2 N
I F p 2 ; F f n exp2i ( hun kvn lwn )
2
sin cos n 1
46.6 53.4
Cd : Te :
112.4 127.6
1 : 1.0009 49.8 : 50.2
* Make powder
diffraction and list
sin2: index the
pattern! Assume it is
cubic
SC BCC FCC Diamond
sin2
s s s s close
0.0462 1 0.0462 2 0.0231 3 0.0154 3 0.0154
0.1194 2 0.0597 4 0.02985 4 0.02985 8 0.01493
Very 0.1615 3 0.05383 6 0.02692 8 0.02019 11 0.01468
weak 0.179 4 0.04475 8 0.02237 11 0.01627 16 0.01119
0.234 5 0.0468 10 0.0234 12 0.0195 19 0.01232
0.275 6 0.04583 12 0.02292 16 0.01719 24 0.01146
0.346 8 0.04325 14 0.02471 18 0.01922 27 0.01281
0.391 9 0.04344 16 0.02444 20 0.01955 32 0.01222
0.461 10 0.0461 18 0.02561 24 0.01921 35 0.01317
0.504 11 0.04582 20 0.0252 27 0.01867 40 0.0126
0.575 12 0.04792 22 0.02614 32 0.01797 43 0.01337
0.616 13 0.04738 24 0.02567 35 0.0176 49 0.01257
0.688 14 0.04914 26 0.02646 36 0.01911 51 0.01349
0.729 16 0.04556 30 0.0243 40 0.01822 56 0.01302
0.799 17 0.047 32 0.02497 43 0.01858 59 0.01354
sin 2 sin 2 sin 2 sin 2
s s s s
Diamond structure and Zinc blend structure:
forbidden peaks! Which one has more peaks?
removing line 4 first
0.0462 3 0.0154
0.1194 8 0.01493
0.1615 11 0.01468
0.234 16 0.01463
0.275 19 0.01447
0.346 24 0.01442
0.391 27 0.01448 very
0.461 32 0.01441
0.504 35 0.0144 close
0.575 40 0.01437
2
0.616 43 0.01433
2
0.01413
0.688 49 0.01404 4a
0.729 51 0.01429 1.542
0.799 56 0.01427 a 6.486 A
0.84 59 0.01424 2 0.01413
Alternative:
Assume the first line is from s = 1, s = 2 and s = 3,
sin 2 2 sin 2 3 sin 2
sin 2
0.0462 0.0462 0.0462
0.0462 1.000 1 2.000 2 3.000 3 3
0.1198 2.593 2 5.189 4 7.779 4 8
0.1615 3.496 3 6.991 6 10.487 8 11
0.179 3.874 4 7.749 8 11.623 11 16
0.234 5.065 5 10.130 10 15.195 12 19
0.275 5.952 6 11.905 12 17.857 16 24
0.346 7.489 8 14.978 14 22.468 18 27
0.391 8.463 9 16.926 16 25.390 20 32
0.461 9.978 10 19.957 18 29.935 24 35
0.504 10.909 11 21.818 20 32.727 27 40
0.575 12.446 12 24.892 22 37.338 32 43
0.616 13.333 13 26.667 24 40.000 35 49
0.688 14.892 14 29.784 26 44.675 36 51
0.729 15.779 16 31.558 30 47.338 40 56
0.799 17.294 17 34.589 32 51.883 43 59
Larger error smaller , use the first three lines to
fit a more correct A.
0.01444, Use this number
to divide sin2 ! sin 2
sin 2 / 0.01444 0.01428
0.0462 3.199 3 3.235
0.1198 8.296 8 8.389
0.1615 11.184 11 11.310
0.179 12.396 16 12.535
0.234 16.205 19 16.387
0.275 19.044 24 19.258
0.346 23.961 27 24.230
0.391 27.078 32 27.381
0.461 31.925 35 . 32.283
0.504 34.903 40 35.294
.
0.575 39.820 43 40.266
42.659 49 . 43.137
Larger 0.616
Deviation0.688 47.645 51 48.179
0.729 50.485 56 51.050 New A is 0.01428
0.799 55.332 59 55.952
0.1790/0.01413 = 12.66; 222 s = 12
(forbidden diffraction lines for diamond structure,
OK for zinc-blend structure!)
* = 5.82 g/cm3 then
VC (6.486)3 5.82
nM 953.67
1.66054 1.66054
M for CdTe is 112.4+127.6 = 240 n = 3.97 ~ 4
There are 4 Cd and 4 Te atoms in a unit cell.
2 2
when h, k, l all odd Fhkl 16( f Cd f Te )
ZnS Cd at 000 & Te at + fcc translations
2i ( h k l )
1 1 1
Fhkl FFCC f Cd fTee 4 4 4 Unmixed hkl only
2 2 2
when h + k + l is odd Fhkl 16( f Cd f Te )
when h + k + l
2 2
= odd multiple of 2 Fhkl 16( f Cd f Te )
2 2
= even multiple of 2 Fhkl 16( f Cd f Te )
sin
0.0 0.2 0.4 0.6 0.8 1.0 1.2
Cd 48 37.7 27.5 21.8 17.6 14.3 12.0
Te 52 41.3 30.3 24.0 19.5 16.0 13.3
fCd + fTe = 100 and |fCd fTe| = 4 at sin / = 0 to
fCd + fTe = 30.3 and |fCd fTe| = 1.7 at sin / ~ 1.0
sin
0.0 0.2 0.4 0.6 0.8 1.0 1.2
RCd Te 625 482 426 415 381 318 379
fCd fTe 2 R
Several hundreds
fCd fTe 2 Cd Te
order disorder
temperature
low TC high
disordered ordered
Complete Disordered structure:
1 1
2i ( h k l 0 )
1 1
2i ( h k 0 l ) 2i ( h 0 k l )
1 1
Fhkl f av 1 e 2 2 e 2 2
e 2 2
rA FA
S
1 FA
complete order: rA = 1 S = 1;
complete disorder: rA = FA S = 0
0S1
AuCu3 : order parameter S
Average atomic factor for A-site
rAu S (1 FAu ) FAu 0.75S 0.25
A-site is the 000 equipoint
rAu :fraction of Au atoms in 000 site
the average atomic form factor
(1 rAu ) f Au ( 2 rAu ) f Cu
f avB
3 3
rB FB
S
1 FB
fZn
fav
fCu
disordered ordered
* Completely random: a BCC structure
1 1 1
2i ( h k l )
2i ( h 0 k 0 l 0 )
Fhkl f av e f av e 2 2 2
f av (1 ei ( h k l ) )
f av 0.5 f Cu 0.5 f Zn
0
T TC
Relative intensity from the superlattice line and
the fundamental line:
* Case AuCu3: ignoring the multiplication factor and
Lorentz-polarization factor, just look at the |F|2.
Intensity (superlattice line) | f Au f Cu |2
Intensity (Fundamental line) | f Au 3 f Cu |2
Assume sin/ = 0 f = z
Intensity (superlattice line) | 79 29 |2
~ 0.09
Intensity (Fundamental line) | 79 3 29 | 2
Produce extra
difference in
fCu fZn