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XRay Diffraction
XRay Diffraction
X- Ray Sources
Diffraction: Bragg’s Law
Crystal Structure Determination
Kα
Characteristic radiation →
White Kβ due to energy transitions
Intensity
Mo 0.71
Cu 1.54
Co 1.79
Fe 1.94
Cr 2.29
Incident X-rays
SPECIMEN Heat
Fluorescent X-rays
Electrons
Scattered X-rays
Compton recoil Photoelectrons
Transmitted beam
X-rays can also be refracted (refractive index slightly less than 1) and reflected (at very small angles)
Incoherent Scattering (Compton modified) From loosely bound charges
Here the particle picture of the electron & photon comes handy
2θ
E2 = hν 2 (λ2 ,ν 2 )
∆λ = λ2 − λ1 = 0.0243(1 − Cos 2θ )
Energy
E L3
levels L 3
E L2 L2
E L1 L1
Characteristic x-rays
EK K (Fluorescent X-rays)
(10−16 s later → seems like scattering!)
Nucleus
A beam of X-rays directed at a crystal interacts with the
electrons of the atoms in the crystal
The electrons oscillate under the influence of the incoming
X-Rays and become secondary sources of EM radiation
The secondary radiation is in all directions
The waves emitted by the electrons have the same frequency
as the incoming X-rays ⇒ coherent
The emission will undergo constructive or destructive
interference
Secondary
Incoming X-rays emission
Sets Electron cloud into oscillation Sets nucleus into oscillation
Small effect → neglected
Oscillating charge re-radiates In phase with the incoming x-rays
BRAGG’s EQUATION
Deviation = 2θ
Ray 1
Ray 2 θ θ
θ
θθ d
dS
in θ
X Y
Atomic Planes
X Y
Bragg’s equation is a negative law
If Bragg’s eq. is NOT satisfied → NO reflection can occur
If Bragg’s eq. is satisfied → reflection MAY occur
Diffraction = Reinforced Coherent Scattering
Reflection Diffraction
Occurs from surface Occurs throughout the bulk
n Sinθ θ
a a
d hkl = d 220 = d 220 1
8 =
h2 + k 2 + l 2 d110 2
a
d110 =
2
In XRD nth order reflection from (h k l) is considered as 1st order reflection
from (nh nk nl)
nλ = 2d hkl sin θ
d hkl
λ=2 sin θ
n
λ = 2d nh nk nl sin θ
Crystal structure determination
Single θ
LAUE
Panchromatic X-rays
TECHNIQUE
ROTATING
Monochromatic X-rays θ Varied by rotation CRYSTAL
METHOD
THE POWDER METHOD
λ = 2dSinθ
d= a
h +k +l
2 2 2
4a sin θ
2 2
λ = 2
2
h +k +l 2 2
2
4a
(h + k + l ) = 2 sin θ
2 2 2 2
λ
(h + k + l ) ∝ sin θ
2 2 2 2
Intensity of the Scattered electrons
A B C
Scattering by a crystal Electron Atom Unit cell (uc)
A Scattering by an Electron
Em
issi
(λ0 ,ν 0 ) on
in all
d irec
Sets electron into oscillation tio ns
Coherent
(definite phase relationship) (λ0 ,ν 0 ) Scattered beams
For an polarized wave
z
P
For a wave oscillating in z direction α r
e 4 Sin 2α
I = I 0 2 4 2
mc r
For an unpolarized wave E is the measure of the amplitude of the wave
E2 = Intensityc
E 2 = E y2 + E z2
I0
= I0 y = I0z
2
I Py = I 0 y
4
e Sin ( ) = I
2 π
2 e4 1
2 4 2
m 2c 4 0y
r2 m c r
I Pz = I 0 z
4
e Sin (
2 π
2
− 2θ ) = I e 4 Cos 2 ( 2θ )
2 4
m 2c 4 0z
r2 mc r 2
4
I +
e 0 y 0zI Cos 2
( 2θ )
I P = I Py + I Pz = 2 4
m c r2
I 0 e 4 1 + Cos 2 ( 2θ )
IP =
2 4 2
⇒ Scattered beam is not unpolarized
2 mc r
Very small number
Rotational symmetry about x axis + mirror symmetry about yz plane
Forward and backward scattered intensity higher than at 90°
Scattered intensity minute fraction of the incident intensity
f → 10
Z↑ ↑ ↓
Sin(θ ) / λ ↓ ↑ ↓
C Scattering by the Unit cell (uc)
Coherent Scattering
Unit Cell (uc) representative of the crystal structure
Scattered waves from various atoms in the uc interfere to create the diffraction pattern
The wave scattered from the middle plane is out of phase with the ones
scattered from top and bottom planes
Ray 1 = R1 R1'
Ray 3 = R3 R3'
θ B A θ
x
R S
Ray 2 = R2 B R2'
d(h00)
M N a
(h00) plane
C
Unit Cell
a
AC = d h 00 =
h
MCN :: AC :: λ
RBS :: AB :: x
AB x x
= =
AC λ a
h
Structure factor is independent of the shape and size of the unit cell
niπ
Structure factor calculations e = (−1) n
Simple Cubic
A Atom at (0,0,0) and equivalent positions e ( odd n ) iπ = −1
e ( even n ) iπ = +1
e niπ = e − niπ
e iθ + e − iθ
= Cos (θ )
2
iϕ j i[ 2π ( h x′j + k y ′j + h z ′j )]
F = fj e = fj e
iϕ j i[ 2π ( h x′j + k y ′j + h z ′j )]
F = fj e = fj e
1 1
i[ 2π ( h ⋅ + k ⋅ + h ⋅ 0 )]
F = f ei[ 2π ( h ⋅0+ k ⋅0+ h⋅0 )] + f e 2 2
h +k
i [ 2π ( )]
= f e0 + f e 2
= f [1 + e iπ ( h + k ) ]
Real
(h + k) e
ve n
r b o t h odd F =2f F2 = 4 f 2
en o
Both ev
e.g. (001), (110), (112); (021), (022), (023)
F = f [1 + e iπ ( h + k ) ] Mixtu
r e of odd
a nd e ve n
( h + k)
odd F =0 F2 = 0
e.g. (100), (101), (102); (031), (032), (033)
iϕ j i[ 2π ( h x′j + k y ′j + h z ′j )]
F = fj e = fj e
1 1 1
i[ 2π ( h ⋅ + k ⋅ + h ⋅ )]
F = f ei[ 2π ( h⋅0+ k ⋅0+ h⋅0 )] + f e 2 2 2
h + k +l
i [ 2π ( )]
= f e0 + f e 2
= f [1 + e iπ ( h + k +l ) ]
Real
l ) ev en F =2f F2 = 4 f 2
(h + k +
e.g. (110), (200), (211); (220), (022), (310)
F = f [1 + e iπ ( h + k +l ) ] (h + k +
l ) odd
F =0 F2 = 0
e.g. (100), (001), (111); (210), (032), (133)
D Atom at (0,0,0) & (½, ½, 0) and equivalent positions Face Centred Cubic
F = f [1 + e iπ ( h + k ) + e iπ ( k +l ) + e iπ ( l + h ) ]
(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)
E
Na+ at (0,0,0) + Face Centering Translations → (½, ½, 0), (½, 0, ½), (0, ½, ½)
Cl− at (½, 0, 0) + FCT → (0, ½, 0), (0, 0, ½), (½, ½, ½) NaCl:
i[ 2π ( 0 )] i[ 2π ( h +2 k )] i[ 2π ( k 2+l )] i[ 2π ( l +2h )] Face Centred Cubic
F = f Na + e +e +e +e +
i[ 2π ( h2 )] i[ 2π ( k2 )] i[ 2π ( 2l )] i[ 2π ( h +2k +l )]
f Cl − e +e +e +e
F = f Na + [1 + eiπ ( h + k ) + eiπ ( k +l ) + eiπ ( l + h ) ] +
f Cl − [eiπ ( h ) + eiπ ( k ) + eiπ ( l ) + eiπ ( h + k +l ) ]
(h, k, l) unmixed F = 4[ f Na + + f Cl − e iπ ( h + k +l ) ]
F = 4[ f Na + + f Cl − ] If (h + k + l) is even F 2 = 16[ f Na + + f Cl − ]2
F = 4[ f Na + − f Cl − ] If (h + k + l) is odd F 2 = 16[ f Na + − f Cl − ]2
⇒ Presence of additional atoms/ions/molecules in the uc (as a part of the motif ) can alter the
intensities of some of the reflections
Relative Intensity of diffraction lines in a powder pattern
(
I P = 1 + Cos 2 ( 2θ ) )
Lorentz factor Combination of 3 geometric factors
1 1
Lorentz factor = ( Cosθ )
Sin 2θ Sin 2θ
(
I P = 1 + Cos 2 ( 2θ ) ) 1
Lorentz factor =
1
( Cosθ )
Sin 2θ Sin 2θ
1 + Cos 2 ( 230
θ)
Lorentz Polarizati on factor =
Sin θ Cosθ
2
25
Lorentz-Polarization factor
20
15
10
5
Intensity of powder pattern lines (ignoring Temperature & Absorption factors)
Valid for Debye-Scherrer geometry
2 1 + Cos 2θ
2
I = F p I → Relative Integrated “Intensity”
Sin θ Cosθ
2
F → Structure factor
p → Multiplicity factor
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
Crystal = Lattice + Motif
Diffraction Pattern
* 1 * 1 * 1
b1 = ( a2 × a3 ) b2 = ( a3 × a1 ) b3 = ( a1 × a2 )
V V V
*
*
bi usuall written as ai a3
*
b3
* 1
b = b3 = ( a1 × a2 )
*
3
V C
Area (OXMB ) 1 a2
= =
Area (OXMB ) ⋅ Height of Cell OP
P
1
b = *
3
d 001 B
a1 M
The reciprocal lattice is created by interplanar spacings
A reciprocal lattice vector is ⊥ to the corresponding real lattice plane
* * * *
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
* 1
g *
hkl = g hkl =
d hkl
Planes in the crystal become lattice points in the reciprocal lattice
ALTERNATE CONSTRUCTION OF THE REAL LATTICE
Reciprocal lattice point represents the orientation and spacing of a set of
planes
Reciprocal Lattice
(01) 02 12 22
a2 (11)
(10) 01 11
* * * 21
b2 g11 g 21
(21)
a1
a1 * 1
b1 a1
10 20
00 The reciprocal lattice has an origin!
22
(01) 12
02
(11) 21
a2 (10) 11
(21) 0 1*
a1 b2
a1 * 20
22
b1 10
12
02
(01)
00
21
11
01 (11)
(10)
Note perpendicularity of various vectors
(21) 20
10
Reciprocal lattice is the reciprocal of a primitive lattice and is purely
geometrical does not deal with the intensities of the points
Physics comes in from the following:
For non-primitive cells (• lattices with additional points) and for crystals
decorated with motifs (• crystal = lattice + motif) the Reciprocal lattice
points have to be weighed in with the corresponding scattering power (|
Fhkl |2)
Some of the Reciprocal lattice points go missing (or may be scaled up
or down in intensity)
Making of Reciprocal Crystal (Reciprocal lattice decorated with a
motif of scattering power)
The Ewald sphere construction further can select those points which are
actually observed in a diffraction experiment
Examples of 3D Reciprocal Lattices weighed in with scattering power (|F|2)
SC
001
011
101 111
Lattice = SC 000
010
100
110
No missing reflections
Reciprocal Lattice = SC
011
101
020
000
Lattice = BCC 110
200
100 missing reflection (F = 0) 220
F2 = 4 f 2
Figures NOT to Scale
002
022
FCC
202
222
111
020
000
Lattice = FCC
200
220
100 missing reflection (F = 0)
110 missing reflection (F = 0)
Weighing factor for each point “motif”
Reciprocal Lattice = BCC
F 2 = 16 f 2
Figures NOT to Scale
The Ewald* Sphere
The reciprocal lattice points are the values of momentum transfer for
which the Bragg’s equation is satisfied
For diffraction to occur the scattering vector must be equal to a
reciprocal lattice vector
Geometrically ⇒ if the origin of reciprocal space is placed at the tip of ki
then diffraction will occur only for those reciprocal lattice points that lie
on the surface of the Ewald sphere
aul Peter Ewald (German physicist and crystallographer; 1888-1985) See Cullity’s book: A15-4
Ewald Sphere
Reciprocal Space
01
∆ K(41)
= K =g = Diffraction Vector
Diffraction cones and the Debye-Scherrer geometry
http://www.matter.org.uk/diffraction/x-ray/powder_method.htm
Powder diffraction pattern from Al Radiation: Cu Kα , λ = 1.54 Å
111
Note:
Peaks or not idealized δ peaks → broadend
Increasing splitting of peaks with ↑g θ
Peaks are all not of same intensity
311
220
200
331
422
420
222
400
SC 1 2 3 4 5 6 8 …
BCC 1 2 3 4 5 6 7 …
FCC 3 4 8 11 12 …
DC 3 8 11 16 …
2θ → θ Intensity Sinθ Sin2 θ ratio
FCC
h2 + k2 + l2 SC FCC BCC DC
1 100
2 110 110
3 111 111 111
4 200 200 200
5 210
6 211 211
7
8 220 220 220 220
9 300, 221
10 310 310
11 311 311 311
12 222 222 222
13 320
14 321 321
15
16 400 400 400 400
17 410, 322
18 411, 330 411, 330
19 331 331 331
Consider the compound ZnS (sphalerite). Sulphur atoms occupy fcc sites with zinc atoms
displaced by ¼ ¼ ¼ 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 ½ ½, ½ 0 ½, ½ ½ 0 i.e. in the fcc position and 4 atoms of type B at the sites ¼
¼ ¼ from the A sites. This can be expressed as:
(
I P = 1 + Cos 2 ( 2θ ) )
Long range order Combination of 3 geometric factors
1 1
Lorentz factor = ( Cosθ )
Sin 2θ Sin 2θ
0 90 180
Diffraction angle (2θ ) →
Monoatomic gas
Intensity →
Diffraction angle (2θ ) → Diffraction angle (2θ ) →
Liquid300 310
/ Amorphous solid
Intensity →
0 90 1
0 90 180