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XRD Intensity Factors

What defines the intensity and


presence/absense of some beams?
This is dictated by the position of the atoms in the lattice. Thus the
crystal structure plays a role (and also the number and type of each
atom).

What defines the intensity and


presence/absense of some beams?
To understand how intensities varies for the different peaks we need
to look at the interaction of X-Rays with the crystal.
This can be understood by considering the interaction of X-Rays with
an electron, then an atom (group of electrons since X-rays do not
interact with the nucleus), and finally a crystal (group of atoms with
added periodicity)

Scattering by electron
X-Rays are electromagnetic radiation, this is, they have mutually
perpendicular electric and magnetic felds. Electrons are negatively
charged particles that are affected by these electric and magnetic
felds. When X-Rays interact with electrons, they cause it to oscillate.
The oscillating electron will in turn emit X-rays. This is called
scattering.

Scattering by electron
There are 2 kinds of scattering:
1. Coherent scattering: emitted X-rays have the same wavelength
(same energy) as the incident X-rays. This is also called elastic
scattering. The scattered radiation has a definite phase relation with
the incident X-rays.
2. Incoherent scattering: the X-rays lose some energy during
scattering, so the final energy is lower (wavelength is higher) than
the incident energy. There is no definite phase relation to the
incident radiation. This is also called inelastic scattering.

Elastic Scattering
For elastic scattering, the scattered radiation is phase-shifted from
the incident beam by /2 or has a path difference of /2.
The scattering takes place in all directions, yet the intensity depends
on the angle of scattering.

Elastic Scattering
The expression for this is given by J.J. Thompson.

where, is the intensity at a distance r from the electron and is


the angle between the recoiling electron and the scattered x-ray. In
the case of diffraction we want the intensity in terms of the angle
between the incident and scattered radiation (2).

Elastic Scattering

This is the Thompson equation for the scattering of x-rays by a single


electron. The intensity decreases as square of the distance from the
electron. Scattering is high in the forward or backward direction
(2 = 0 180). The term (1 + 2/2 ) is called the
polarization factor.

Structure factor with a single atom basis

Using equation 7 it is possible to calculate the structure factor for a


() plane of any unit cell, once the atom scattering factors and
positions are known. The structure factor is related to the intensity of
the x-ray diffracted from that plane. Thus if the structure factor for a
given plane is zero then there will be no diffracted intensity, even
though Bragg's law is satisfied. Thus, Bragg's law only decides the 2
value for a given plane while structure factor decides the intensity.

Simple Cubic (SC)


In a simple cubic unit cell there is only one atom per unit cell, located
at (000). So = 1 and () is (000). So using equation 7 the
structure factor for a () plane simply becomes = . Thus,
for a simple cubic structure diffraction is possible for all possible
planes since the structure factor is a constant, equal to the atomic
scattering factor. Thus, all planes can be seen in the diffraction
pattern of a simple cubic structure.

NOTE. The intensities are still not the same since there are other
factors involved.

Body Centered Cubic (BCC)


In a body centered cubic structure there are 2 atoms per unit cell, at
(000) and (, , ). These represent the fractional coordinates of
the atoms in the unit cell. Substituting them in equation 7 we can get
the expression for the structure factor as:

Thus, diffraction intensities are only found for specific planes in


bcc which satisfy the condition in equation 10 (i.e. + + should
be even).

Face centered cubic (FCC)


In the face centered cubic structure there are 4 atoms per unit cell,
one at the corner and 3 on the face centers. Once again using
equation 7, the expression for the structure factore simplifies to:

Thus, for fcc structure, diffraction lines are seen for planes like
(111), (200), (220), (311), (222) where the indices are all even or
odd.

Hexagonal close packed (HCP)


In the case of the hcp structure, the fractional coordinates for atoms
are 000 and (1 3 , 2 3 , 1 2). The equation for the structure factor
then becomes:

Structure factor
The structure factor only depends on the position and type of atoms
in the unit cell. The calculations derived before are for unit cells with
only one type of atom. If we have more than one type of atom, then
the atomic scattering factors are also different and the structure
factor rules are no longer valid.

X-Ray Intensity
In the absence of all other factors the intensity of the diffracted X-ray
is equal to the square of the structure factor. But there are a number
of other factors that affect the intensity.

Multiplicity Factor
Relative proportion of the planes contributing to diffraction. The
more the number of planes, greater is the intensity.
Compare diffraction from the (100) and (111) set of planes of a cubic
crystal. The (100) family has 3 planes (100), (010), and (001) with the
same d-spacing (hence same 2) but different orientations. The 111
family has 4 planes with the same d-spacing but different orientation:
(1,1,1), (-1,1,1), (1,-1,1), (1,1,-1).

Multiplicity Factor
Thus, everything else being same, the ratio of the intensities from the
(100) and (111) planes will be in the ratio of 3/4. Different planes
have different multiplicity values, which are usually tabulated. The
multiplicity factor depends on the crystal structure since the planes
must have the same d-spacing.

Lorentz-polarization Factor
The Lorentz factor is a trigonometric factor that relates to the
distribution of planes as a function of 2.
For a powder simple, with randomly oriented particles, the integrated
intensity of a reflection at a given Bragg angle depends on the
number of particles with that orientation.

Lorentz-polarization Factor
Even though the particles are oriented at random, this number is not
a constant but depends on the value of the Bragg angle. This
dependence is called the Lorentz factor and is given by:

Lorentz-polarization Factor
Usually, the Lorentz factor is combined with the polarization factor to
form the Lorentz-polarization Factor:

Lorentz-polarization Factor
The Lorentz-polarization factor as a function of a Bragg angle is shown
by:

Absorption Factor
The X-ray intensity also depends on the absorption of the specimen
being investigated. This also depends on the geometry of the setup.
In the case of the diffractometer, the absorption factor is independent
of the Bragg angle and does not affects the relative intensities of the
different lines.

Temperature Factor
Atoms in the lattic are constantly vibrating about their equilibrium
posotion. As the temperatura increases, this vibration amplitude does
so. One effect of this vibration is that lattice spacing constantly
changes, thus the overall intensity of a line decreases by increasing
the temperature.
For a given temperature, the effect is pronounced at higher Bragg
angles since the d-spacing is smaller. The temperature effect is usually
determined experimentally and written in the form exp 2 .

X-ray Intensity
Putting the various other factors together, the intensity of the X-ray
diffraction line is given by:

refers to the relative integrated intensity, is the Structure Factor


for the plane and is the Multiplicity Factor. The other factors
are the Lorentz-polarization and temperature factors. The absoprtion
factor is not included for the relative intensisties since it does not
depends on the Bragg angle.
NOTE. If there is any preferred orientation due to external conditions,
like growth or stress, then this equation is no longer valid.

Reference:
http://mme.iitm.ac.in/swamnthn/sites/default/files/Lec6.pdf