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XRD Theory
XRD Theory
Technique Write-up
X-Ray Diffraction
The crystal structure is studied through the diffraction of photons, neutron
and electrons. The diffraction pattern depends on the crystal structure and the
wavelength of the incident x-ray beam. When the wavelength of the incident
radiation is comparable with or smaller than the lattice constant of the crystal,
diffracted beams are obtained in directions different from the incident direction.
W.L. Bragg put forward a simple explanation of the diffracted beams from
a crystal:
Suppose that the incident waves are reflected specularly from parallel
planes of atoms in the crystal, with each plane reflecting only a very small
fraction of the radiation, like a silvered mirror. In specular (mirror like) reflection
the angle of incidence is equal to the angle of reflection. The diffracted beams
are found when the reflections from parallel planes of atoms interfere
constructively, as in Fig 1. We treat elastic scattering, in which the energy of the
x-ray is not changed on scattering.
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Indraneel Samanta
PHY 550
Technique Write-up
This equation is known as the Bragg Law. Bragg reflection can occur only for
wavelength 2d. This is why we cannot use visible light.
Although the reflection from each plane is specular, only for certain values
of will the reflections from all parallel planes add up in phase to give a strong
reflected beam. If each plane were perfectly reflecting, only the first plane of a
parallel set would see the radiation and any wavelength would be reflected.
The Bragg Law is a consequence of the periodicity of the lattice but is
independent of the composition of the basis of atoms associated with every
lattice point. However the composition of the basis atoms determine the relative
intensity of the various orders of diffraction for a given set of parallel planes.
Introduction of the concept of reciprocal space.
The concept of reciprocal space is very important in the study of diffraction
patterns. The reason may be addressed as follows.
Vector algebra is very convenient for describing otherwise complicated
diffraction problems and the reciprocal lattice offers a simple approach to
handling diffraction in terms of vectors. Again the use of the reciprocal lattice
permits the analysis of diffraction problems that cannot be accessed by Braggs
Law (example: off-peak scattering). Moreover the reciprocal lattice is important in
all phases of solid state physics, so an understanding of this concept is useful in
and of itself.
Let us consider a real space unit cell with real lattice basis vectors a, b
and c. now, we can define a set of reciprocal lattice basis vectors by:
1
(b c ) = b c
V
a (b c )
1
b = (c a )
V
1
c = (a b )
V
a =
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Indraneel Samanta
PHY 550
Technique Write-up
Just like we can define a real space lattice in terms of our real space
lattice vectors, we can define a reciprocal space lattice in terms of our reciprocal
space lattice vectors:
r = h a + kb + lc
The reciprocal space lattice vectors form an orthonormal set:
a b = a c = 0
a a = 1
= a (b c
V V = 1
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Indraneel Samanta
PHY 550
Technique Write-up
Diffraction Conditions:
The set of reciprocal vectors G determines the possible x-ray reflections.
From Fig.2 it is obvious that the difference in phase factor is exp [i (k-k ). r]
between beams scattered from volume elements r apart. The wavevectors of the
incoming and the outgoing beams are k and k. The amplitude of the wave
scattered from a volume element is proportional to the local electron
concentration n(r). The total amplitude of the scattered wave in the direction of k
is proportional to the integral over the crystal of n(r) dV times the phase factor
exp [i (k-k ).r].
Crystal
Specimen
dV
O
Incident Beam
eik.r
Outgoing Beam
eik.r
r
Figure 2 The difference in path length of the incident wave 'k' at the point O, r is r sin, and the
difference in phase angle is (2r sin)/, which is equal to k.r. For the diffracted wave the difference
in phase angle is -k .r the total difference in phase angle is (k-k). r and the wave scattered from dV
at r has the phase factor exp [i (k-k).r], relative to the wave scattered from a volume element
at the origin O
dV n(r) exp[-ik.r]
.(1)
Where k+k = k.
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Indraneel Samanta
PHY 550
Technique Write-up
k measures the change in wavevector and is called the scattering vector. As per
discussion in Introduction to Solid State Physics by Charles Kittel, the Fourier
components of n(r) is given by:
n(r) = nG exp (iG.r)
.(2)
dV nG exp ( i(G-k) . r )
(3)
From the above equation it is evident that the scattering amplitude is maximum
when k = G. Again from Braggs law we know that - as X-rays are scattered by
the atoms in a set of crystal planes, a maximum in the scattered amplitude (i.e.
all scattered waves have the same phase) occurs when:
n = 2d sin
Hence one can say that the two key equations to x-ray diffraction may be defined
as k = G & n
= 2d sin
.
Laue Construction:
The original result of diffraction theory, namely k = G , may be expressed
in another way to give the Laue equations, which are valuable for their
geometrical representation.
Now, the scalar product of both k & G successively with a1, a2 , a3 gives
a1 . k = 2v1 ;
a2 . k = 2v2
; a3 . k = 2v3
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Indraneel Samanta
PHY 550
Technique Write-up
G
2
The Ewald construction (Fig.3), done by P.P. Ewald, helps us to visualize the
requirements to satisfy the diffraction condition in three dimensions.
The points on the RHS are the reciprocal lattice points of the crystal. The
vector k is drawn in the directionof the incident x-ray beam and the origin is
chosen such that k terminates at any reciprocal lattice point. Here a sphere has
been drawn with radius k = 2/ abouit the origin of k. A diffracted beam will be
formed if this sphere intersects any other point in the reciprocal lattice. Thje
sphere as drawn intercepts a point connected with the end of k by a reciprocal
lattice vector G. The diffracted x-ray beam is in the direction k = k +G. The angle
is the Braggs angle.
Reflection from a single plane of atoms takes place in the directions of the
lines of intersection of two cones, for examplethe cones defined by the first two of
Laues equations.
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Indraneel Samanta
PHY 550
Technique Write-up
As mentioned above it should be emphasized on the fact that all x-ray diffraction
experiments are based on the two main equations:
k = G
&
2dSin
= n
The three most common techniques that we use for the study of thin films are
1. -2 scan or the phase measurements
2. The Rocking Curve.
3. The Diffraction Space Map.
In case of phase measurements, for a fixed wavelength of incident x-ray
beam, the magnitude of k is held perpendicular to the sample surface while a
scan is perfoirmed for the selection of 2
for a maximum value of k.
A crystal is rotated (or rocked) through the Bragg angle B, while the
beam reflected byit is measured in a fixed counter with a wide slit. The resulting
curve of intensity vs is called a rocking curve. In this case the magnitude of k
is held constant and a scan in 2 is performed to optimize k.
In case of charting out the Diffraction Space-map both the magnitude and
the direction k are variedto perform a scan.
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Indraneel Samanta