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Chapter 3c X Ray Diffraction
Chapter 3c X Ray Diffraction
X- Ray Sources
Diffraction: Braggs Law
Crystal Structure Determination
Part of
MATERIALS SCIENCE
& A Learners Guide
ENGINEERING
AN INTRODUCTORY E-BOOK
Recommended websites:
http://www.matter.org.uk/diffraction/
http://www.ngsir.netfirms.com/englishhtm/Diffraction.htm
What other uses can XRD be put to apart from crystal structure determination?
Grain size determination Strain in the material
Some Basics
For electromagnetic radiation to be diffracted* the spacing in the grating (~a series
of obstacles or a series of scatterers) should be of the same order as the
wavelength.
In crystals the typical interatomic spacing ~ 2-3 ** so the suitable radiation
for the diffraction study of crystals is X-rays.
Hence, X-rays are used for the investigation of crystal structures.
Neutrons and Electrons are also used for diffraction studies from materials.
Neutron diffraction is especially useful for studying the magnetic ordering in
materials.
** If the wavelength is of the order of the lattice spacing, then diffraction effects will be prominent.
** Lattice parameter of Cu (aCu) = 3.61
dhkl is equal to aCu or less than that (e.g. d111 = aCu/3 = 2.08 )
Generation of X-rays
X-rays can be generated by decelerating electrons.
Hence, X-rays are generated by bombarding a target (say Cu) with an electron beam.
The resultant spectrum of X-rays generated (i.e. X-rays versus Intensity plot) is shown in
the next slide. The pattern shows intense peaks on a broad background.
The intense peaks can be thought of as monochromatic radiation and be used for X-ray
diffraction studies.
Beam of electrons
Target
X-rays
Intensity
K
White
radiation
K
Characteristic radiation
due to energy transitions
in the atom
0.2
0.6
1.0
Of K
radiation ()
Mo
0.71
Cu
1.54
Co
1.79
Fe
1.94
Cr
2.29
1.4
Wavelength ()
The high intensity nearly monochromatic K x-rays can be used as a radiation source for
X-ray diffraction (XRD) studies a monochromator can be used to further decrease the
spread of wavelengths in the X-ray
Incident X-rays
SPECIMEN
Fluorescent X-rays
Electrons
Scattered X-rays
Coherent
From bound charges
Absorption (Heat)
Compton recoil
Photoelectrons
Transmitted beam
X-rays can also be refracted (refractive index slightly less than 1) and reflected (at very small angles)
Diffraction
Now we shall consider the important topic as to how X-rays interact with a
crystalline array (of atoms, ions etc.) to give rise to the phenomenon known as Xray diffraction (XRD).
Let us consider a special case of diffraction a case where we get sharp[1]
diffraction peaks.
Diffraction (with sharp peaks) (with XRD being a specific case) requires three important conditions to
be satisfied:
Coherent, monochromatic, parallel waves (with wavelength ).
Crystalline array of scatterers* with spacing of the order of (~) .
Fraunhofer diffraction geometry
Coherent, monochromatic, parallel wave
Aspects related to the wave
Diffraction pattern
with sharp peaks
Crystalline*,**
Fraunhofer diffraction geometry implies that parallel waves are impinging on the scatteres
(the object), and the screen (to capture the diffraction pattern) is placed far away from the
object.
Click here to know more about Fraunhofer and Fresnel diffraction geometries
Secondary
emission
Incoming X-rays
Schematics
Let us consider a coherent wave of X-rays impinging on a crystal with atomic planes at an
angle to the rays.
Incident and scattered waves are in phase if the:
i) in-plane scattering is in phase and
ii) scattering from across the planes is in phase.
Atomic Planes
A B
BRAGGs EQUATION
A portion of the crystal is shown for clarity- actually, for destructive interference to occur
many planes are required (and the interaction volume of x-rays is large as compared to that shown in the schematic).
The scattering planes have a spacing d.
Ray-2 travels an extra path as compared to Ray-1 (= ABC). The path difference between
Ray-1 and Ray-2 = ABC = (d Sin + d Sin) = (2d.Sin).
For constructive interference, this path difference should be an integral multiple of :
The previous page explained how constructive interference occurs. How about the rays just
of Bragg angle? Obviously the path difference would be just off as in the figure below.
How come these rays go missing?
Click here to understand how
destructive interference of
just of-Bragg rays occur
Reflection
Diffraction
The interplanar spacing appears in the Braggs equation, but not the interatomic
spacing a along the plane (which had forced incident = scattered); but we are not
free to move the atoms along the plane randomly click here to know more.
For large interplanar spacing the angle of reflection tends towards zero as d increases,
Sin decreases (and so does ).
The smallest interplanar spacing from which Bragg diffraction can be obtained is /2
maximum value of is 90, Sin is 1 from Bragg equation d = /2.
Sin = n/2d
0.34
20.7
0.69
Cubic crystal
hkl
d nh nk nl
d nh nk nl
a
h2 k 2 l 2
a
d hkl
2
2
2
n
n h k l
a
e.g.
a
d 220
8
a
d110
2
d 220 1
d110 2
In XRD nth order reflection from (h k l) is considered as 1st order reflection from (nh nk nl)
n 2d hkl sin
d hkl
2
sin
n
2d nh nk nl sin
d nhnk nl
d hkl
1
n
Hence, (100) planes are a subset of (200) planes
d 200 1
d100 2
d 300 1
d100 3
Funda Check How is it that we are able to get information about lattice parameters of the order
of Angstroms (atoms which are so closely spaced) using XRD?
Funda Check
is the angle between the incident x-rays and the set of parallel atomic planes (which have
a spacing dhkl). Which is 10 in the above figure.
It is NOT the angle between the x-rays and the sample surface (note: specimens could be
spherical or could have a rough surface).
2 d100
1.54
0.244 100 14.149
2(3.15)
The missing reflection is due to the presence of additional atoms in the unit cell
(which are positions at lattice points) which we shall consider next
However, the second order reflection from (100) planes (which is equivalent to the first order
reflection from the (200) planes is observed
Sin100
2
1.54
0.488
2 d100 3.15
2nd order
100
1nd order
200
29.267
This is because if the green rays have a path difference of 2 then the red ray will have path
difference of which will still lead to constructive interference!
Important
points
A
Electron Polarization factor
B
Atom Atomic scattering factor (f)
C
Unit cell (uc) Structure factor (F)
Click here to know more about
Bravais Lattice
Simple
all
None
Body centred
(h + k + l) even
(h + k + l) odd
Face centred
h, k and l unmixed
h, k and l mixed
h and k unmixed
h and k mixed
Bravais Lattice
Allowed Reflections
SC
All
BCC
(h + k + l) even
FCC
h, k and l unmixed
DC
Allowed reflections
in SC*, FCC*, BCC*
& DC crystals
h2 + k2 + l2
SC
100
110
111
111
200
200
210
211
FCC
BCC
DC
110
111
200
211
220
220
300, 221
10
310
11
311
311
12
222
222
13
320
14
321
220
220
310
311
222
321
15
16
400
17
410, 322
18
411, 330
19
331
400
400
400
411, 330
331
331
The ratio of (h2 + k2 + l2) derived from extinction rules (previous page)
As we shall see soon the ratios of (h2 + k2 + l2) is proportional to Sin2
which can be used in the determination of the lattice type
SC
BCC
FCC
11
12
DC
11
16
Note that we have to consider the ratio of only two lines to distinguish FCC and DC. I.e. if the
ratios are 3:4 then the lattice is FCC.
But, to distinguish between SC and BCC we have to go to 7 lines!
Monochromatic X-rays
Panchromatic X-rays
Monochromatic X-rays
Many s (orientations)
Powder specimen
Single
Varied by rotation
POWDER
METHOD
fixed
variable
LAUE
TECHNIQUE
variable
fixed
ROTATING
CRYSTAL
METHOD
fixed
rotated
Only the powder method (which is commonly used in materials science) will be considered in this text.
2 d Sin
Cubic crystal
(1)
d Cubic
a
2
2
2
h k l
(2) in (1)
2
2
4
a
sin
2
2
h k2 l2
a
2
2
4 sin 2
(h 2 k 2 l 2 )
(h 2 k 2 l 2 )
4a 2
sin 2
(h 2 k 2 l 2 ) sin 2
(2)
POWDER METHOD
In the powder sample there are crystallites in different random orientations (a polycrystalline
sample too has grains in different orientations)
The coherent x-ray beam is diffracted by these crystallites at various angles to the incident direction
All the diffracted beams (called reflections) from a single plane, but from different crystallites lie
on a cone.
Depending on the angle there are forward and back reflection cones.
A diffractometer can record the angle of these reflections along with the intensities of the reflection
The X-ray source and diffractometer move in arcs of a circle- maintaining the Bragg reflection
geometry as in the figure (right)
Different cones
for different
reflections
Random assemblage of
crystallites in a material
As the scan takes place at increasing
angles, planes with suitable d,
which diffract are picked out from
favourably oriented crystallites
h2
hkl
Sin()
100
4.00
0.19
11.10
110
2.83
0.27
15.80
111
2.31
0.33
19.48
200
2.00
0.39
22.64
210
1.79
0.43
25.50
211
1.63
0.47
28.13
220
1.41
0.54
32.99
300
1.33
0.58
35.27
10
310
1.26
0.61
37.50
Increasing
Intensity
Sin
Sin2
ratio
Radiation: Cu K, = 1.54
Note:
This is a schematic pattern
In real patterns peaks or not idealized peaks broadened
Increasing splitting of peaks with g
(1 & 2 peaks get resolved in the high angle peaks)
Radiation: Cu K, = 1.54
400
222
311
220
200
111
Note:
Peaks or not idealized peaks broadened
Increasing splitting of peaks with g
Peaks are all not of same intensity
Funda Check
How are real diffraction patterns different from the ideal computed ones?
We have seen real and ideal diffraction patterns. In ideal patterns the peaks are
functions.
Real diffraction patterns are different from ideal ones in the following ways:
Peaks are broadened
Could be due to instrumental, residual non-uniform strain (microstrain), grain size etc. broadening.
Funda Check
Ans: 90
Funda Check
1) smaller the wavelength of the X-rays, more will be the number of peaks possible.
2) Lattice type in SC we will get more peaks as compared to (say) FCC/DC. Other things being
equal.
3) Lower the symmetry of the crystal, more the number of peaks (e.g., in tetragonal crystal
the 100 peak will lie at a different 2 as compared to the 001 peak).
2dSin
2dmin
Sin max
d min
Solved example
Let us assume that we have the 2 versus intensity plot from a diffractometer
To know the lattice type we need only the position of the peaks (as tabulated below)
#
Sin
Sin2
ratio
Index
38.52
19.26
0.33
0.11
111
2.34
44.76
22.38
0.38
0.14
200
2.03
65.14
32.57
0.54
0.29
220
1.43
78.26
39.13
0.63
0.40
11
311
1.22
82.47
41.235
0.66
0.43
12
222
1.17
99.11
49.555
0.76
0.58
16
400
1.01
112.03
56.015
0.83
0.69
19
331
0.93
116.60
58.3
0.85
0.72
20
420
0.91
137.47
68.735
0.93
0.87
24
422
0.83
10
163.78
81.89
0.99
0.98
27
333
0.78
Using 2 d Sin
o
a 4.04 A Al
FCC
a
0.33
3
Note
(h 2 k 2 l 2 ) sin 2
Note: Error in d spacing decreases with so we should use high angle lines for lattice parameter calculation
Click here to know more
XRD_lattice_parameter_calculation.ppt
Solved example
Another example
Given the positions of the Bragg peaks we find the lattice type
Dividing Sin2 by
0.134/3 = 0.044667
Whole
number
ratios
Sin
Sin2
Ratios
of Sin2
21.5
0.366
0.134
25
0.422
0.178
1.33
3.99
37
0.60
0.362
2.70
8.10
45
0.707
0.500
3.73
11.19
11
47
0.731
0.535
11.98
12
58
0.848
0.719
5.37
16.10
16
68
0.927
0.859
6.41
19.23
19
FCC
More Solved
Examples on XRD
Click here
Funda Check We had pointed out that ~ a is preferred for diffraction. Let us see what happens if we drastically increase or decrease .
(This is only a thought experiment!!)
Aluminium
hkl
111
200
220
311
222
400
331
420
422
333
2.34
2.03
1.43
1.22
1.17
1.01
0.93
0.91
0.83
0.78
= 1.54
Sin()
0.33
19.26
0.38
=3
Sin()
38.52
0.64
39.87
22.38
44.76
0.74
0.54
32.57
65.14
0.63
39.13
0.66
= 0.1
Sin()
79.74
0.02
1.22
2.45
47.64
95.28
0.02
1.41
2.82
1.05
0.03
2.00
4.01
78.26
1.23
0.04
2.35
4.70
41.24
82.47
1.28
0.04
2.45
4.90
0.76
49.56
99.11
1.49
0.05
2.84
5.68
0.83
56.02
112.03
1.61
0.05
3.08
6.16
0.85
58.30
116.60
1.65
0.05
3.15
6.30
0.93
68.74
137.47
1.81
0.06
3.45
6.91
0.99
81.89
163.78
1.92
0.06
3.68
7.35
If we make small
all the peaks get
crowded to small
angles
Applications of XRD
Bravais lattice determination
We have already seen these applications
Lattice parameter determination
Determination of solvus line in phase diagrams
Long range order
Crystallite size and Strain
Next slide
Intensity
0
Crystal
90
180
Intensity
Monoatomic gas
No peak
Intensity
90
0
Diffuse Peak
90
180
180
Note
Sharp peaks are missing
Broad diffuse peak survives
the peak corresponds to the average spacing between atoms which the diffraction experiment picks
out
(XRD patterns) courtesy: Dr. Kallol Mondal, MSE, IITK
Funda Check
Cubic crystal
d hkl
a
h2 k 2 l 2
d13
a
10
d 34
a
a
25 5
d10
a
d12
5
a
a
1
d11
a
2