x-ray and electron diffraction

➢ X-ray scattering
➢ Factors affecting intensities of diffracted beams

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Factors that affect the diffracted intensity

Structure factor
Polarization factor
Lorentz factor
Multiplicity factor
Temperature factor
absorption factor

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Single electron
scattering
➢ An unpolarized X-ray beam traveling in say x-
direction is scattered by an bound electron of an
atom.

➢ The incident electric field causes the electron to

accelerate/decelerate which then re-radiates.
( )
the 1 + cos 2 2 / 2 term is
called the polarization factor
K  1 + cos 2 2 
I P= I 0 2  
r  2  2
 e2 
K =  2  4

 mc 
 X-rays are scattered in all directions after interaction with the atoms

J.J Thomson stated that the intensity of the scattered beam by a

single electron of charge e, mass m and r the distance in meters
from the electron is

α is the angle between the scattering direction and the direction of

acceleration of the electron.
Coherent Scattering of x-ray by a The incident beam is traveling in the direction Ox and encounters an
single electron electron at 0.

The unpolarized incident beam, has its electric vector E in a random direction in the yz plane. This beam may be
resolved into two plane polarized components, having electric vectors Ey and Ez.

E2 = E2y + E2z; Ey = Ez; E2y= E2z = ½ E2

I α A2 Therefore, Ioy = Ioz = ½ Io

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 SCATTERING BY AN
ATOM
➢An atom with atomic number Z is surrounded with Z electrons, all of which
can scatter X-rays
➢Since an atom has a finite size, there will be a difference in the path
traveled (i.e. a phase difference) in the X-rays scattered from different
locations around the atom

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 SCATTERING BY AN ATOM

➢The atomic scattering factor f is defined as:

amplitude scattered by Z electrons in an atom
f =
amplitude scattered by a single electron

❖ The atomic scattering factor f = Z for any atom in the

forward direction (2 = 0)  (=) =
❖ As  increases f decreases → functional dependence of
the decrease depends on the details of the distribution of
electrons around an atom (sometimes called the form
factor)

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 SCATTERING BY A UNIT
CELL

scattering by an single electron

is modified by

scattering by an collection of electrons

is modified by

scattering by an collection of atoms

➢ The structure factor is the amplitude scattered per unit

structure, or the amplitude scattered by a unit cell

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 Scattering by a unit cell- the structure factor

❖ Just like path differences (and their resultant phase differences)

modulate the scattered amplitude from the electrons in an atom,
the path/phase differences introduced by the atoms within a unit
cell will alter the scattered amplitude as well
❖ We can calculate the amplitude of x-rays scattered from a
collections of atoms located on each lattice point, for a primitive
lattice.
❖ We can rewrite the amplitude equation to include other atoms in a
unit cell

❖ The resultant wave scattered by all the atoms of the unit cell is
called structure factor –

✓ because It describes how the atom arrangement, given by their

fractional coordinates [uvw] for each atom affect the scattered
intensity.
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 The structure factor
• The structure factor for a particular hkl reflection is given by:

( )
J
Fhkl =  f je
2 π i hu j + kv j + lw j

amplitude scattered by all atoms in a unit cell

Fhkl =
amplitude scattered by a single electron

• The intensity of a Bragg reflection is therefore proportional

to the square of the structure factor:


I  Fhkl F = Fhkl
2
hkl F may be complex, but “I” must be real!

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 A SIMPLE EXAMPLE – PRIMITIVE UNIT
CELL
WITH ONE ATOM
Let the atom be placed at 000 (remember that we can define
the unit cell any way we want)

N
Fhkl =  f n e 2 i (hun + kvn +lwn )
1
= fe 2 i (h0+ k 0+l 0 )
= f

so Fhkl = f 2
2

In this case the structure factor is independent of h, k and l;

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 BODY CENTERED CUBIC
UNIT CELL
• The bcc crystal structure has atoms at 000 and ½½½:

N
Fhkl =  f n e 2 i ( hun + kvn +lwn )
1

( )
the atoms are the
same, so the atomic = f e 2 i ( h0+ k 0+l 0 ) + e 2 i ( h / 2+ k / 2+l / 2 )
= f (1 + e )
scattering factor i ( h + k + l )
can be factored out

2f for h+k+l = an even integer

So Fhkl =
0 for h+k+l = an odd integer

(200), (400), (220)   Fhkl = 4 f 2

2

“forbidden”
(100), (111), (300)   Fhkl = 0
2

reflections
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 FACE CENTERED CUBIC UNIT
CELL
The fcc crystal structure has atoms at 000, ½½0, ½0½ and 0½½:
N
Fhkl =  f n e 2 i ( hun + kvn +lwn )
1

(
= f 1 + e i ( h + k ) + e i ( h +l ) + e i ( k +l ) )

• If h, k and l are all even or all odd numbers (“unmixed”), then the
exponential terms all equal to +1  F = 4f
• If h, k and l are mixed even and odd, then two of the exponential
terms will equal -1 while one will equal +1  F = 0

16f 2, h, k and l unmixed even and odd

Fhkl =
2

0, h, k and l mixed even and odd 18

 Each of the crystal system
is derivable from the other
by a simple shift of one
Base centered atom by the vector ½ C.
orthorhombic unit
cell Body centered orthorhombic unit cell
1 1’ 1 1’
3’ 3’
 
2’
  2’
2 2
D F
A C A E C
B B
a
Diffraction from the (001) planes of base centered and
body centered orthorhombic lattice
The path difference between rays 1’ and 2’ is one wavelength. The rays are in
phase.
The path difference between 1’ and 3’ is exactly one half wavelength and
annul each other. 19

The positions of the atoms in the unit cell affect the intensities.
Permitted
Reflections

Simple Cubic (100), (110), (111), (200), (210), (211),

(220), (300), (221) … Sequence: 1, 2, 3, 4,
5, 6, 8, 9,10 …..
BCC (110), (200), (211), (220), (310),
(222)….Sequence: 2, 4, 6, 8, 10, 12, 14…..
FCC (111), (200), (220), (311)…..
…Sequence:3, 4, 8, 11,12,16…
DC (111), (220), (311), (400)……Sequence:
3, 8, 11,16…
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 Structure factor conclusions

❖ The scattering power of an atom is dependent on

its atomic number and the direction of
observation. It is also dependent on the
wavelength of the incident beam because the
difference in path length is also important.
❖ In general the scattering factor decreases if
sin/ increases.

This is why at higher angles diffraction intensities

are lower. 21
Relative Intensity of diffraction lines in a powder pattern

Structure Factor (F) Scattering from UC

Multiplicity factor (p) Number of equivalent scattering planes

Polarization factor Effect of wave polarization

(
I P = 1 + Cos 2 (2 ))
Lorentz factor Combination of 3 geometric factors

 1   1 
Lorentz factor =  (Cos ) 
 Sin 2   Sin 2 

Absorption factor Specimen absorption

Temperature factor Thermal diffuse scattering

 Multiplicity factor
The multiplicity factor arises from the fact that in
general there will be several sets of hkl-planes
having different orientations in a crystal but with
the same d and F2 values

100, 1 00, 010, 0 1 0, 001, 00 1 p100 = 6

110, 1 10, 1 1 0, 1 1 0, 101, 10 1 , 1 0 1 , 1 01, 011, 0 1 1, 01 1 , 0 1 1 p110 = 12
111, 11 1 , 1 1 1, 1 11, 1 1 1 , 1 1 1 , 1 1 1, 1 1 1 p111=8

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Multiplicity factor
Lattice Index Multiplicity Planes
Cubic (100) 6 [(100) (010) (001)] ( 2 for negatives)
(with highest
symmetry) (110) 12 [(110) (101) (011), (110) (101) (011)] ( 2 for negatives)

(111) 12 [(111) (111) (111) (111)] ( 2 for negatives)

(210) → 3! Ways, (210) → 3! Ways,
(210) 24*
(210) → 3! Ways, (210) → 3! Ways
(211) → 3 ways, (211) → 3! ways,
(211) 24
(211) → 3 ways
(321) 48*
Tetragonal (100) 4 [(100) (010)] ( 2 for negatives)
(with highest
symmetry) (110) 4 [(110) (110)] ( 2 for negatives)

(111) 8 [(111) (111) (111) (111)] ( 2 for negatives)

(210) = 2 Ways, (210) = 2 Ways,
(210) 8*
(210) = 2 Ways, (210) = 2 Ways
(211) 16 [Same as for (210) = 8]  2 (as l can be +1 or −1)

(321) 16* Same as above (as last digit is anyhow not permuted)

* Altered in crystals with lower symmetry

Multiplicity factor

hkl hhl hk0 hh0 hhh h00

Cubic
48* 24 24* 12 8 6
hk.l hh.l h0.l hk.0 hh.0 h0.0 00.l
Hexagonal
24* 12* 12* 12* 6 6 2
hkl hhl h0l hk0 hh0 h00 00l
Tetragonal
16* 8 8 8* 4 4 2
hkl hk0 h0l 0kl h00 0k0 00l
Orthorhombic
8 4 4 4 2 2 2
hkl h0l 0k0
Monoclinic
4 2 2
hkl
Triclinic
2

* Altered in crystals with lower symmetry (of the same crystal class)
 Lorentz Factor

The reflected intensity of a crystal depends on the on

the experimental setup and this factor is proportional to
1/4sin2cos.
• The combination of geometric corrections are combined
together into a single Lorentz-polarization (LP) factor:

1 + cos 2  1 
2
 1  1 + cos 2 2
 (cos  )  →
 sin 2   sin 2  sin  cos 
2
2
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 THE LORENTZ FACTOR
➢ In a polycrystalline sample, we must also correct for the number of plane
normals that are favorably oriented to diffract:

N r  2r sin (90 −  B )  cos  B

= =
N 4r 2
2
 THE LORENTZ FACTOR
➢ In a polycrystalline sample, the diffracted intensity is spread over a
cone with a base radius of Rsin2B so the relative intensity per unit
length of line is proportional to 1/sin2B
THE LORENTZ-POLARIZATION FACTOR
• The combination of geometric corrections are lumped
together into a single Lorentz-polarization (LP) factor:

1 + cos 2 2  1    + 2
2
(cos  )
1 1 cos
  →
2  sin 2   sin 2  sin 2  cos 

The effect of the LP factor is to decrease

the intensity at intermediate angles and
increase the intensity in the forward and
backwards directions
 THE TEMPERATURE FACTOR
➢ As atoms vibrate about their equilibrium positions in a
crystal, the electron density is spread out over a larger
volume
➢ This causes the atomic scattering factor to decrease with
sin/ (or |S| = 4sin/ )more rapidly than it would
normally:
THE TEMPERATURE FACTOR

The temperature factor is given by:

 sin 2  
exp − B 2 
  
where the thermal factor B is related to the mean square
displacement of the atomic vibration:

B = 8 2  u 2
This is incorporated into the atomic scattering factor:

f → f 0e − M  f 2 ~ e −2 M
Formally, we allow for the effect by defining The temperature
factor is given by: f as the atomic scattering factor of an atom
undergoing thermal vibration
f → f 0e − M

M = 2  u /(sin  /  )
2 2 2

2 the mean square displacement of the atomic vibration

u

This is incorporated into the atomic scattering factor:

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 Absorption factor
• For a flat diffractometer sample in a symmetric geometry,
the absorption factor is independent of angle.
• The total diffracted for an infinitely thick specimen is
given by
I0 A
I =
2

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