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Lecture 6: Intensity of Diffracted Beams
Lecture 6: Intensity of Diffracted Beams
beams
Contents
1 Introduction
2 Scattering by an electron
3 Scattering by an atom
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9
. 9
. 10
. 10
. 11
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7 X-ray intensity
7.1 Multiplicity factor . . . . .
7.2 Lorentz-polarization factor
7.3 Absorption factor . . . . .
7.4 Temperature factor . . . .
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Introduction
Scattering by an electron
Figure 4: Diffraction from 001 and 002 orthorhombic planes. For the body
centered the 001 lines are absent. Taken from Elements of X-ray diffraction
- B.D. Cullity.
are affected by these electric and magnetic fields. When X-rays interact with
electrons it causes it to oscillate. The oscillating electron will in turn emit
X-rays - this is called scattering. 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 and 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 that 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.
In the case of X-ray diffraction we are interested in the elastic scattering component. Any inelastic scattering will only add to the background. Another
component to the background is x-ray fluorescence so the choice of the x-ray
source depends on the type of material (Cu is not normally used for Fe due
to strong x-ray fluorescence). 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 but the intensity depends on the
angle of scattering. The expression for this is given by J.J. Thompson.
Ir = I0
e4
sin2
r2 m2 c4
(1)
(3)
Scattering by an atom
(4)
Figure 7: Atomic scattering factor for Cu. Taken from Elements of X-ray
diffraction - B.D. Cullity.
We started with one electron and them moved onto the atom, which was
considered as a group of electrons (as far as x-ray scattering is considered).
The next step is the unit cell. We can consider the unit cell as a group of
atoms arranged in a periodic fashion. Also we will focus only on the coherent
scattering since incoherent radiation will only add to the background. Given
that the atoms are arranged in a crystal with three dimensional periodicity xray scattering only takes place at certain directions, diffraction, which obeys
Braggs law. If Braggs law is not satisfied then there is no diffraction and
hence no x-ray scattering. Thus, we only need to look at the x-ray intensity
in directions where Braggs law is satisfied and the intensity depends on the
types and positions of the atoms in the lattice. Also, we only have to consider
only one unit cell since the crystal is periodic.
Consider the one set of planes shown in figure 9. For simplicity let these
planes be of the form (h00) planes so that the d-spacing is equal to a\h.
This is from the definition of Miller indices where (hkl) gives the intercepts
of the planes with the axes. X-rays are incident on this plane at the Bragg
angle so that diffraction condition is satisfied. Consider another set of atoms
located at position B, which is at a distance x from A. The path difference
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= 2(hu + kv + lw)
(5)
This represents the phase difference between x-rays reflected from the unit
cell at different positions. Combining this with the atomic scattering factor
of the atoms located at the different positions we can define a new term
called the structure factor, F. The structure factor with an atom located
at position (uvw) in an unit cell is given by
F = f exp 2i(hu + kv + lw)
(6)
If there are N atoms in the unit cell and the nth atom has structure factor
fn and is located at (un vn wn ) then the structure factor for the unit cell, for
some plane (hkl) is given by
F =
N
X
n=1
(7)
(8)
5.1
Simple cubic
In a simple cubic unit cell there is only one atom per unit cell, located at
(000). So N = 1 and (uvw) is (000). So using equation 7 the structure factor
for a (hkl) plane simply becomes Fhkl = f . 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. The intensities are still
not the same since there are other factors involved.
5.2
In a body centered cubic structure there are 2 atoms per unit cell, at (000)
and ( 21 12 21 ). 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
Fhkl = f [1 + exp i(h + k + l)]
(9)
From equation 9 it can be seen that when h+k+l is even (exp i(h + k + l))
is equal to 1 and when h + k + l is odd it is -1. So the structure factor is
h + k + l = even F = 2f
h + k + l = odd F = 0
10
(10)
Thus, diffraction intensities are only found for specific hkl planes in bcc which
satisfy the condition in equation 10 i.e. h + k + l should be even. This can
be seen from figure 1 for bcc Fe. The first line seen is (110) and not (100)
because of the rule in equation 10.
5.3
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 factor simplifies to
Fhkl = f [1 + exp i(h + k) + exp i(k + l) + exp i(l + h)]
(11)
(12)
Thus, for fcc structure diffraction lines are seen for planes like (111), (200),
(220), (311), (222) where the indices are all even or odd. Other diffraction lines are absent. The x-ray plot for Al in figure 2 confirm this rule.
5.4
In the case of the hcp structure, the fractional coordinates for the atoms are
(000) and ( 31 23 21 ). The equation for the structure factor then becomes
Fhkl = f [1 + exp 2i(
h
2k
l
+
+ )]
3
3
2
(13)
While this is a more complicated equation than the equations for fcc and
bcc, it is possible to derive rules for the values of (hkl) to obtain non zero
diffraction intensities.
It is important to understand that the structure factor calculations do not
depend on the size and shape of the unit cell. The structure factor only
depends on the position and type of atoms in the unit cell. The
calculations derived above 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.
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For unit cells with more than one type of atom - compounds or intermetallics
the structure factor can be still calculated using equation 7 except that the
atomic scattering factor for each type of atom needs to be taken into account.
The consequence of this is that the intensities for some (hkl) planes will no
longer be zero but will have a finite value (since the f values are different).
To give and example consider the case of CsCl. This has a bcc structure
with the Cl ions at the corner and the Cs+ ion at the center of the unit cell.
Then the structure factor for this unit cell, using equation 7 is given by
Fh kl = fCl + fCs exp i(h + k + l)
(14)
Using the same conditions for bcc the structure factor values are
h + k + l = even F = fCl + fCs
h + k + l = odd F = fCl fCs
(15)
Thus, unlike a bcc unit cell with one atom basis, the intensity of the diffraction line does not go to zero when h + k + l is odd but has a finite value (the
intensity will be low since it is proportional to the difference of the atomic
scattering factors). Similarly, we can work out the structure factor for NaCl,
which has a fcc structure with a 2 atom basis Na at (000) and Cl at ( 12 12 12 ).
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.
7.1
Multiplicity factor
The multiplicity factor refers to the relative proportion of the planes contributing to diffraction. More the no. 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 - (111), (111), (111), (111).
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.
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7.2
Lorentz-polarization factor
7.3
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 affect the relative intensities of the different lines.
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7.4
Temperature factor
Atoms in the lattice are constantly vibrating about their equilibrium position. As the temperature increases, this vibration amplitude increases. One
effect of this vibration is that the lattice spacing constantly changes so that
the overall intensity of a line decreases with increasing temperature. At the
same time background scattering increases. 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(2M ).
Putting the various factors together the intensity of the x-ray diffraction
line is given by
1 + cos2 2
) exp(2M )
(18)
I = |F 2 |p(
sin2 cos
I here refers to the relative integrated intensity (area under the curve of
the diffraction line), F is the structure factor for the (hkl) plane and p is
the multiplicity factor. The other factors are the Lorentz-polarization factor
and the temperature factor. The absorption factor is not included for the
relative intensities since it does not depend on Bragg angle. The intensity
given here assumes a random polycrystalline sample - powder or film. If
there is any preferred orientation due to external conditions like growth or
stress than this equation is no longer valid. The ICDD (International Center
for Diffraction Data) databases gives the d-spacing and the intensities of the
various diffraction lines of a material. The intensities are given with respect
to the strongest line which has a value of 100. By comparing the experimental
ratios with the values given in the ICDD database it is possible to check if a
sample has a truly random orientation.
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