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X- Ray Sources
Diffraction: Braggs Law
Crystal Structure Determination
Beam of electrons
Target
X-rays
Intensity
K
White
radiation
0.2
0.6
Characteristic radiation
due to energy transitions
in the atom
1.0
Wavelength ()
1.4
Target Metal
Of K radiation ()
Mo
0.71
Cu
1.54
Co
1.79
Fe
1.94
Cr
2.29
Incident X-rays
SPECIMEN
Fluorescent X-rays
Heat
Electrons
Scattered X-rays
Compton recoil
Photoelectrons
Coherent
Incoherent (Compton modified)
From bound charges
From loosely bound charges
Transmitted beam
X-rays can also be refracted (refractive index slightly less than 1) and reflected (at very small angles)
Refraction of X-rays is neglected for now.
E1 h 1
(1 , 1 )
E2 h 2
(2 , 2 )
2 1 0.0243(1 Cos 2 )
No fixed phase relation between the incident and scattered waves
Incoherent does not contribute to diffraction
(Darkens the background of the diffraction patterns)
Fluorescent X-rays
Vacuum
Energy
E
levels L
L3
E L2
L2
E L1
L1
EK
Nucleus
Characteristic x-rays
(Fluorescent X-rays)
(1016s later seems like scattering!)
Incoming X-rays
Secondary
emission
BRAGGs EQUATION
Deviation = 2
Ray 1
Ray 2
dS
in
Note: shift is actually not a problem! Why is systematic shift not a problem?
n AY YB
AY XY Cos[180 ( )] XY Cos ( )
YB XY Cos ( )
d
[2 Sin Sin ] 2 d Sin
Sin
n 2 d Sin
d
Sin( )
XY
XC
Cos 2
a
a Cos 1 a Cos 2 h
a Cos 1 Cos 2 h
Generalizing into 3D
a Cos 1 Cos 2 h
b Cos 3 Cos 4 k
c Cos 5 Cos 6 l
Laues equations
S0 incoming X-ray beam
S Scattered X-ray beam
a (S S0 ) h
b (S S0 ) k
c (S S0 ) l
Diffraction
n = 2d Sin
n is an integer and is the order of the reflection
For Cu K radiation ( = 1.54 ) and d110= 2.22
n
Sin
0.34
20.7
43.92
d hkl
0.69
a
h2 k 2 l 2
a
d 220
8
a
d110
2
d 220 1
d110 2
n 2d hkl sin
d hkl
2
sin
n
2d nh nk nl sin
A
Electron Polarization factor
B
Atom Atomic scattering factor (f)
C
Unit cell (uc) Structure factor (F)
A Scattering by an Electron
(0 , 0 )
Em
issi
on
in
Coherent
(definite phase relationship)
all
di
rec
tion
s
(0 , 0 )
Scattered beams
The electric field (E) is the main cause for the acceleration of the electron
The moving particle radiates most strongly in a direction perpendicular to its
motion
The radiation will be polarized along the direction of its motion
P
r
x
e 4 Sin 2
I I 0 2 4
2
mc r
e 4 Sin 2
I I 0 2 4
2
mc r
E E E
2
2
y
2
z
I0
I0 y I0z
2
2
e 4 Sin y
2 4
2
mc
r
2
e 4 Sin z
I0z 2 4
mc
r
I P I0 2 4
2
mc
r
2
2
e 4 Sin y Sin z
I P I0 2 4
2
mc
r
Sin 2 y Sin 2 z
1 Cos 2 y 1 Cos 2 z 2 Cos 2 y Cos 2 z
Hence
1 Cos 2 (x )
2 Cos 2 y Cos 2 z 2 1 Cos 2 (x )
Cos
(x )
I P I0 2 4
2
mc
r
In terms of 2
2
e 4 1 Cos (2 )
I P I0 2 4
2
mc
r
e 4 Cos 2 2
I I 0 2 4
mc
r2
P
r
2
E 2 E y2 E z2
I0
I0 y I0z
2
IPy = Intensity at point P due to Ey
I Py I 0 y
Sin 2
e
m2c 4
I0 y
e4 1
2 4
2
mc r
Sin
2
e
2
m 2c 4
r2
I0z
e 4 Cos 2 2
2 4
2
mc
r
I P I Py I Pz
I 0 y I 0 z Cos 2 2
e
2 4
m c
I 0 e 4 1 Cos 2 2
IP
2 4
2
2 mc
r
r2
I 0 e 4 1 Cos 2 2
I P 2 2 4
r mc
2
Polarization factor
Comes into being as we used
unpolarized beam
Scattering by an Atom
Scattering by an atom [Atomic number, (path difference suffered by scattering from each e , )]
Scattering by an atom [Z, (, )]
Sin( )
30
20
Schematic
10
0.2
0.4
0.6
0.8
Sin( )
(1)
1.0
Z
Sin() /
Coherent scattering
Incoherent (Compton)
scattering
Scattering by an Atom
BRUSH-UP
The conventional UC has lattice points as the vertices
There may or may not be atoms located at the lattice points
The shape of the UC is a parallelepiped (Greek paralllepipedon) in 3D
There may be additional atoms in the UC due to two reasons:
The chosen UC is non-primitive
The additional atoms may be part of the motif
The wave scattered from the middle plane is out of phase with the ones
scattered from top and bottom planes
R1'
Ray 1 = R1
Ray 3 = R3
B
M
(h00) plane
R
Ray 2 = R2
R3'
R2'
N
C
Unit Cell
d(h00)
AC d h 00
a
h
MCN :: AC ::
RBS :: AB :: x
AB x
x
AC a
h
R1R3 RBS
R1R3
AB
x
a
AC
h
2 x
x
2 h
a
a
h
Extending to 3D
x
fractional coordinate x
a
2 ( h x k y l z )
R1R3 2 h x
2 ( h x k y l z )
In complex notation
E Aei fei[2 ( h x k y l z )]
If atom B is different from atom A the amplitudes must be weighed by the respective
atomic scattering factors (f)
The resultant amplitude of all the waves scattered by all the atoms in the UC gives the
scattering factor for the unit cell
The unit cell scattering factor is called the Structure Factor (F)
Scattering by an unit cell = f(position of the atoms, atomic scattering factors)
F Structure Factor
hkl
n
fj e
j 1
fj e
i[2 ( h xj k y j l z j )]
I F2
j 1
Structure factor is independent of the shape and size of the unit cell
If the UC distorts so do the planes in it!!
Simple Cubic
ni
(1)
e ( odd n ) i 1
e ( even n ) i 1
e ni e ni
e i e i
Cos ( )
2
F fj e
F f
F2 f 2
i j
fj e
ei[2 ( h 0 k 0
l 0)]
i [2 ( h x j k y j l z j )]
f e0 f
F fj e
i j
fj e
i [2 ( h xj k y j l z j )]
F f ei[2 ( h 0 k 0
l 0)]
i[ 2 (
h k
)]
2
f e0 f e
C- centred Orthorhombic
f e
1
1
i [2 ( h k l 0)]
2
2
f [1 ei ( h k ) ]
Real
v en
(h + k) e
oth odd
b
r
o
n
e
Both ev
F f [1 e i ( h k ) ] Mixture
of odd a
nd e ve n
(h + k)
odd
F 2f
F2 4 f 2
F 0
F2 0
If the blue planes are scattering in phase then on C- centering the red planes will scatter out
of phase (with the blue planes- as they bisect them) and hence the (210) reflection will
become extinct
This analysis is consistent with the extinction rules: (h + k) odd is absent
In case of the (310) planes no new translationally equivalent planes are added on lattice
centering this reflection cannot go missing.
This analysis is consistent with the extinction rules: (h + k) even is present
F fj e
i j
fj e
F f ei[2 ( h 0 k 0
f e0 f e
i[ 2 (
Body centred
Orthorhombic
i [2 ( h xj k y j l z j )]
l 0)]
f e
h k l
)]
2
1
1
1
i[2 ( h k l )]
2
2
2
f [1 ei ( h k l ) ]
Real
F f [1 e i ( h k l ) ]
l)
(h + k +
(h + k +
e ve n
l ) odd
F 2f
F2 4 f 2
F 0
F2 0
F fj e
i j
fj e
i [ 2 ( 0 )]
i [ 2 (
(, , 0), (, 0, ), (0, , )
i [2 ( h xj k y j l z j )]
hk
)]
2
i [ 2 (
k l
)]
2
i [ 2 (
l h
)]
2
F fe
e
e
e
f [1 e i ( h k ) e i ( k l ) e i ( l h ) ]
Real
F f [1 e i ( h k ) e i ( k l ) e i ( l h ) ]
(h, k, l) unmixed
F 4f
F 2 16 f 2
e.g. (111), (200), (220), (333), (420)
(h, k, l) mixed
F 0
F2 0
e.g. (100), (211); (210), (032), (033)
Two odd and one even (e.g. 112); two even and one odd (e.g. 122)
Mixed indices
Two odd and one even (e.g. 112); two even and one odd (e.g. 122)
Mixed indices
CASE
CASE A : [1 ei ( e ) ei ( o ) ei ( o ) ] [1 1 1 1] 0
CASE B : [1 ei ( o ) ei (e ) ei ( o ) ] [1 1 1 1] 0
(h, k, l) mixed
Unmixed indices
F 0
F 0
2
CASE A : [1 ei ( e ) ei ( e ) ei ( e ) ] [1 1 1 1] 4
CASE B : [1 ei ( e ) ei ( e ) ei ( e ) ] [1 1 1 1] 4
(h, k, l) unmixed
F 4f
F 2 16 f 2
e.g. (111), (200), (220), (333), (420)
i [ 2 (
hk
)]
2
i [ 2 (
k l
)]
2
i [ 2 (
l h
)]
2
F f Na e i[ 2 ( 0)] e
e
e
i[ 2 ( h2 )] i[ 2 ( k2 )] i[ 2 ( 2l )] i[ 2 ( h 2k l )]
f Cl e
e
e
e
F f Na [1 e i ( h k ) e i ( k l ) e i ( l h ) ]
f Cl [e i ( h ) e i ( k ) e i ( l ) e i ( h k l ) ]
F f Na [1 e i ( h k ) e i ( k l ) e i ( l h ) ]
f Cl e i ( h k l ) [e i ( k l ) e i ( l h ) e i ( h k ) 1]
F [ f Na f Cl e i ( h k l ) ][1 e i ( h k ) e i ( k l ) e i ( l h ) ]
F [ f Na f Cl e i ( h k l ) ][1 e i ( h k ) e i ( k l ) e i ( l h ) ]
F [Term 1][Term 2]
Mixed indices
Mixed indices
CASE A : Term 2 [1 e i ( e ) e i ( o ) e i ( o ) ] [1 1 1 1] 0
CASE B : Term 2 [1 e i ( o ) e i ( e ) e i ( o ) ] [1 1 1 1] 0
(h, k, l) mixed
F 0
F2 0
Unmixed indices
CASE A : Term 2 [1 e i ( e ) e i ( e ) e i ( e ) ] [1 1 1 1] 4
CASE B : Term 2 [1 e i ( e ) e i ( e ) e i ( e ) ] [1 1 1 1] 4
(h, k, l) unmixed
F 4[ f Na f Cl e i ( h k l ) ]
e.g. (111), (222); (133), (244)
F 4[ f Na f Cl ]
If (h + k + l) is even
F 2 16[ f Na f Cl ]2
e.g. (222),(244)
F 4[ f Na f Cl ]
If (h + k + l) is odd
F 2 16[ f Na f Cl ]2
e.g. (111), (133)
Reflections which
may be present
Reflections
necessarily absent
Simple
all
None
Body centred
(h + k + l) even
(h + k + l) odd
Face centred
h, k and l unmixed
h, k and l mixed
End centred
h and k unmixed
C centred
h and k mixed
C centred
Bravais Lattice
Allowed Reflections
SC
All
BCC
(h + k + l) even
FCC
h, k and l unmixed
DC
h2 + k2 + l2
SC
FCC
100
110
111
111
200
200
210
211
BCC
DC
110
111
200
211
7
8
220
220
300, 221
10
310
11
311
311
12
222
222
13
320
14
321
220
220
310
311
222
321
15
16
400
17
410, 322
18
411, 330
19
331
400
400
400
411, 330
331
331
Reciprocal Lattice
BASIS
VECTORS
* 1
b1 a2 a3
V
*
*
bi usuall written as ai
* 1
b2 a3 a1
V
*
b3
* 1
b b3 a1 a2
V
Area (OAMB)
1
1
b
d 001
*
3
* 1
b3 a1 a2
V
a3
a2
B
B
b3 is to a1 and a2
O
M
A
a1
*
*
*
*
g hkl h b1 k b2 l b3
The length of a reciprocal lattice vector is the reciprocal of the spacing of the
corresponding real lattice plane
*
hkl
*
1
g hkl
d hkl
Reciprocal Lattice
02
(01)
a2
(11)
(21)
a1
a1
(10)
12
22
11
01
*
b2
00
*
b1
*
11
21
*
g 21
10
20
a1
(01)
a2
(11)
(10)
(21)
a1
a1
*
b2
*
b1
(01)
(11)
(21)
(10)
Diffraction Pattern
Position of the Lattice points
LATTICE
SC
001
011
101
Lattice = SC
111
000
010
100
110
No missing reflections
Reciprocal Crystal = SC
002
022
BCC
202
222
011
101
000
Lattice = BCC
020
110
200
100 missing reflection (F = 0)
Weighing factor for each point motif
220
F2 4 f 2
Figures NOT to Scale
002
022
FCC
202
222
111
Lattice = FCC
020
000
200
220
110 missing reflection (F = 0)
F 2 16 f 2
Figures NOT to Scale
High T disordered
BCC
G = H TS
470C
Sublattice-1
Sublattice-2
Low T ordered
SC
Ordered
BCC
SC
Disordered
Ordered
- NiAl, BCC
B2 (CsCl type)
- Ni3Al, FCC
FCC
Ordered
FCC
SC
BCC
1) Construct the lattice and decorate each lattice point with appropriate intensity
2) Use the concept as that for the real crystal
7. Paul-Peter-Ewald-Kolloquium
Freitag, 17. Juli 2008 organisiert von:
Max-Planck-Institut fr Metallforschung
Institut fr Theoretische und Angewandte Physik,
Institut fr Metallkunde,
Institut fr Nichtmetallische Anorganische
Materialien
der Universitt Stuttgart
Programm
13:30
13:45
14:00
14:30
15:00
Pause
Kaffee und Getrnke
15:30
16:00
16:15
ab 17:00
2 1 d hkl
d hkl
2
*
1
*
g hkl
g hkl
d hkl
Sin hkl
2 1 d hkl
Ewald Sphere
Reciprocal Space
Ki
KD
02
01
00
K
10
20
(41)
K = K = g = Diffraction Vector
(Cu K) = 1.54 , 1/ = 0.65 1 (2/ = 1.3 1), aAl = 4.05 , d111 = 2.34 , 1/d111 = 0.43 1
Monochromatic X-rays
Many s (orientations)
Powder specimen
POWDER
METHOD
Panchromatic X-rays
Single
LAUE
TECHNIQUE
Varied by rotation
ROTATING
CRYSTAL
METHOD
Monochromatic X-rays
POWDER METHOD
Diffraction cones and the Debye-Scherrer geometry
Different cones for different reflections
http://www.matter.org.uk/diffraction/x-ray/powder_method.htm
2dSin
Cubic crystal
d Cubic
a
h2 k 2 l 2
2
2
4
a
sin
2
2
h k2 l2
2
4
a
(h 2 k 2 l 2 ) 2 sin 2
2
2
2
a2
(
h
l
)
2
4 sin
(h 2 k 2 l 2 ) sin 2
Scattering from UC
Polarization factor
I P 1 Cos 2 2
Lorentz factor
1
1
Lorentz factor
Cos
Sin 2
Sin 2
Absorption factor
Specimen absorption
Temperature factor
Multiplicity factor
Lattice
Index
Multiplicity
Planes
Cubic
(with highest
symmetry)
(100)
(110)
12
(111)
12
(210)
24*
(211)
24
(321)
48*
(100)
(110)
(111)
(210)
8*
(211)
16
(321)
16*
Tetragonal
(with highest
symmetry)
Multiplicity factor
Cubic
Hexagonal
Tetragonal
Orthorhombic
Monoclinic
Triclinic
hkl
48*
hk.l
24*
hkl
16*
hkl
8
hkl
4
hkl
2
hhl
24
hh.l
12*
hhl
8
hk0
4
h0l
2
hk0
24*
h0.l
12*
h0l
8
h0l
4
0k0
2
hh0
12
hk.0
12*
hk0
8*
0kl
4
hhh
8
hh.0
6
hh0
4
h00
2
h00
6
h0.0
6
h00
4
0k0
2
* Altered in crystals with lower symmetry (of the same crystal class)
00.l
2
00l
2
00l
2
Lorentz factor
Polarization factor
I P 1 Cos 2 2
1
1
Cos
Sin 2
Sin 2
Lorentz factor
1 Cos 2 2
I F p
2
Sin Cos
POINTS
As one is interested in relative (integrated) intensities of the lines constant factors
are omitted
Volume of specimen me , e (1/dectector radius)
Random orientation of crystals in a with Texture intensities are modified
I is really diffracted energy (as Intensity is Energy/area/time)
Ignoring Temperature & Absorption factors valid for lines close-by in pattern
2dSin
Cubic crystal
d Cubic
a
h2 k 2 l 2
2
2
4
a
sin
2
2
h k2 l2
2
4
a
(h 2 k 2 l 2 ) 2 sin 2
2
2
2
a2
(
h
l
)
2
4 sin
(h 2 k 2 l 2 ) sin 2
Intensity
Sin
Sin2
ratio
Intensity
Sin
Sin2
ratio
21.5
0.366
0.134
25
0.422
0.178
37
0.60
0.362
45
0.707
0.500
11
47
0.731
0.535
12
58
0.848
0.719
16
68
0.927
0.859
19
FCC
h2 + k2 + l2
SC
FCC
100
110
111
111
200
200
210
211
BCC
DC
110
111
200
211
7
8
220
220
300, 221
10
310
11
311
311
12
222
222
13
320
14
321
220
220
310
311
222
321
15
16
400
17
410, 322
18
411, 330
19
331
400
400
400
411, 330
331
331
SC
BCC
FCC
11
12
DC
11
16
Radiation: Cu K, = 1.54056
111
422
420
331
400
222
311
220
200
Note:
Peaks or not idealized peaks broadened
Increasing splitting of peaks with g
Peaks are all not of same intensity
n 2 d Sin
d
2 d Cos
d
d
1
d 2 d Cos
Sin
Sin2
ratio
Index
a (nm)
38.52
19.26
0.33
0.11
111
0.40448
44.76
22.38
0.38
0.14
200
0.40457
65.14
32.57
0.54
0.29
220
0.40471
78.26
39.13
0.63
0.40
11
311
0.40480
5*
82.47
41.235
0.66
0.43
12
222
0.40480
6*
99.11
49.555
0.76
0.58
16
400
0.40485
7*
112.03
56.015
0.83
0.69
19
331
0.40491
8*
116.60
58.3
0.85
0.72
20
420
0.40491
9*
137.47
68.735
0.93
0.87
24
422
0.40494
2 Sin
d (d ) Cos
d
2Sin 2
d ( d ) Cos
d
d
d
Sin
Tan
Error in d spacing
Fo
r
the
sa
me
t
he
err
or
in
Si
n
wi
th
d ( d ) Cos
d
d
d
Sin
Tan
Error in d spacing
Applications of XRD
Bravais lattice determination
Lattice parameter determination
Determination of solvus line in phase diagrams
Long range order
Crystallite size and Strain
More
Intensity
Crystal
90
180
Monoatomic gas
Intensity
Intensity
90
180
90
180
Unresolved 1 , 2 peaks
Non-monochromaticity of the source (finite width of peak)
Imperfect focusing
Crystallite size
Strain
Bc
Bs
Stacking fault
In principle every defect contributes to some broadening
Other defects
Crystallite size
Size > 10 m
Spotty ring
No ring pattern
Diffuse
Broadened Rings
Single crystal
Spotty pattern
Ring pattern
Broadened Rings
B Bi Bc Bs Br
Longer tail
Br2 B 2 Bi2
Br2 ( B Bi ) B 2 Bi2
http://en.wikipedia.org/wiki/Carl_Friedrich_Gauss
Scherrers formula
Wavelength
k
Bc
L Average crystallite size ( to surface of specimen)
L Cos ( B )
Strain broadening
Bs Tan( B )
Strain in the material
Br Bc Bs
Br
k
Bs Tan ( )
Bc
L Cos ( )
k
Tan ( )
L Cos ( )
Br Cos ( )
k
Sin( )
L
Example of a calculation
Intensity
Sample: Annealed Al
Radiation: Cu k ( = 1.54 )
Sample: Cold-worked Al
Radiation: Cu k ( = 1.54 )
40
60
Intensity
2
X-Ray Diffraction: A Practical Approach, C. Suryanarayana & M. Grant Norton, Plenum Press, New York (1998)
40
60
Annealed Al
Peak No.
2 ()
hkl
Bi = FWHM ()
Bi = FWHM (rad)
38.52
111
0.103
1.8 103
44.76
200
0.066
1.2 103
65.13
220
0.089
1.6 103
Cold-worked Al
2 ()
Sin()
hkl
B ()
B (rad)
Br2 B 2 Bi2
Br Cos (rad)
1 38.51
0.3298
111
0.187
3.3 103
2.8 103
2.6 103
2 44.77
0.3808
200
0.206
3.6 103
3.4 103
3.1 103
3 65.15
0.5384
220
0.271
4.7 103
4.4 103
3.7 103
k
1.7 10 3
L
Grain Size ( L) 90 nm
end
Iso-intensity circle
Extinction Rules
Structure Factor (F): The resultant wave scattered by all atoms of
the unit cell
The Structure Factor is independent of the shape and size of
the unit cell; but is dependent on the position of the atoms
within the cell
Consider the compound ZnS (sphalerite). Sulphur atoms occupy fcc sites with zinc atoms
displaced by from these sites. Click on the animation opposite to show this structure.
The unit cell can be reduced to four atoms of sulphur and 4 atoms of zinc.
Many important compounds adopt this structure. Examples include ZnS, GaAs, InSb, InP
and (AlGa)As. Diamond also has this structure, with C atoms replacing all the Zn and S
atoms. Important semiconductor materials silicon and germanium have the same structure as
diamond.
Structure factor calculation
Consider a general unit cell for this type of structure. It can be reduced to 4 atoms of type
A at 000, 0 , 0 , 0 i.e. in the fcc position and 4 atoms of type B at the sites
from the A sites. This can be expressed as:
421 missing
0.65
0.28
Multiplicity factor
Lattice
Index
Multiplicity
Planes
Cubic
with highest
symmetry
(100)
(110)
12
(111)
(210)
24
(211)
24
(321)
48
(100)
[(100) (010)]
(110)
[(110) ( 110)]
(111)
(210)
(211)
24
(321)
48
Tetragonal