Professional Documents
Culture Documents
Chapter 3c X Ray Diffraction
Chapter 3c X Ray Diffraction
Chapter 3c X Ray Diffraction
Recommended websites:
http://www.matter.org.uk/diffraction/
http://www.ngsir.netfirms.com/englishhtm/Diffraction.htm
Caution Note: In any chapter, amongst the first few pages (say 5 pages) there will be some ‘big picture’
overview information. This may lead to ‘overloading’ and readers who find this ‘uncomfortable’ may skip
particular slides in the first reading and come back to them later.
What will you learn in this ‘sub-chapter’?
How to produce monochromatic X-rays?
How does a crystal scatter these X-rays to give a diffraction pattern?
Bragg’s equation
What determines the position of the XRD peaks? Answer) the lattice.
What determines the intensity of the XRD peaks? Answer) the motif.
How to analyze a powder pattern to get information about the lattice type?
(Cubic crystal types).
What other uses can XRD be put to apart from crystal structure determination?
Grain size determination Strain in the material Determination of solvus line in
phase diagrams.
** If the wavelength is of the order of the lattice spacing, then diffraction effects will be prominent.
Three possibilities (regimes) exist based on the wavelength () and the spacing between the scatteres (a).
< a transmission dominated.
~ a diffraction dominated.
Click here to know more
> a reflection dominated.
Target Of K
White K Metal radiation (Å)
Intensity
radiation Mo 0.71
Characteristic radiation → Cu 1.54
due to energy transitions
Co 1.79
in the atom
Fe 1.94
Cr 2.29
C. Gordon Darwin, Grandson of C. Robert Darwin developed the dynamic theory of scattering of x-rays (a tough theory!) in 1912
When X-rays impinge on a specimen, the interaction can result in various signals/emissions/
effects.
The coherently scattered X-rays are the ones important from a XRD perspective.
The interaction of the incident X-rays with loosely bound charges leads to incoherent
scattering of X-rays (also refered to as Compton modified X-rays).
The incident X-rays may knock off of a core level electron of atoms of the material, followed
by the transition of an electron from a higher level. This leads to the emission of ‘secondary’
X-rays the fluorescent X-rays.
Incident X-rays may also knock out electrons from the material (Compton recoil and
photoelectrons).
Incident X-rays
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 X-
ray 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:
Radiation related Coherent, monochromatic, parallel waves
& (with wavelength ).
Sample related Crystalline array of scatterers* with spacing of the order of (~) .
Diffraction geometry related Fraunhofer diffraction geometry (& this is actually part of the Fraunhofer geometry)
** With a de Broglie wavelength Click here to know more about Fraunhofer and Fresnel diffraction geometries
XRD the first step
A beam of X-rays directed at a crystal interacts with the electrons of the atoms in the crystal.
The electrons oscillate under the influence of the incoming X-Rays and become secondary sources
of EM radiation.
The secondary radiation is in all directions.
The waves emitted by the electrons have the same frequency as the incoming X-rays coherent.
The emission can undergo constructive or destructive interference.
Secondary
Incoming X-rays emission
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.
*Max von Laue’s postulate: If (i) crystals have a periodic arrangement of atoms and if
(ii) x-rays of waves (concepts which were not confirmed till then), then crystals should act
like a diffraction grating for x-rays. Both these postulates (i & ii) were proved by a single
experiment by Laue (published in 1912 which won him the noble prize in 1914).
Let us consider in-plane scattering
A B
X Y
Atomic Planes
X Y
Warning: we are using ray diagrams in spite of
BRAGG’s EQUATION being in the realm of ‘physical optics’ Let us consider scattering across planes
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 :
n = 2d Sin the Bragg’s equation. (More about this sooner).
The path difference between Ray-1 and Ray-3 is = 2(2d.Sin) = 2n = 2n. This implies that if Ray-1
and Ray-2 constructively interfere Ray-1 and Ray-3 will also constructively interfere. (And so forth).
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. This will not lead to complete destructive interference and hence this ‘ray’
should exist !
How come these “rays”, which are just of the Bragg angle, ‘go missing’?
The explanation can be found in the link: understanding diffraction.
Briefly, as we go deeper into the crystal we will accrue path differences and the ray from
plane-1 will be exactly out of phase (path difference of /2) with a ray scattered from this
‘deep seated plane’ and hence will ‘go missing’.
*Sir William Henry Bragg and William Lawrence Bragg (this won the father and son team the noble prize in
1915).
Since there are two Braggs involved, wherever we
refer to the law or the equation it has be Braggs’ (and
[1] not Bragg’s as I have done in this chapter)
[1]
Note: X-rays can ALSO be reflected at very small angles of incidence Planes are imaginary constructs
Jump
Quantum If n = 2d Sin is the Bragg’s equation, then what is the (famous) Braggs’ law?
Braggs Law
The diffracted beam appears to be specularly reflected from a set of crystal lattice planes.
Angle of incidence = Angle of reflection.
Understanding the Braggs’ equation
n = 2d Sin
The equation is written better with some descriptive subscripts:
This (hkl) is in real space and hence the brackets we will soon drop this brackets!
n Sin = n/2d
d300 1
d100 3
Note:
Technically, in Miller indices we factor out the common factors. Hence, (220) 2(110) (110).
In XRD we extend the usual concept of Miller indices to include planes, which do not pass through
lattice points (e.g. every alternate plane belonging to the (002) set does not pass through lattice points)
and we allow the common factors to remain in the indices.
I have seen diagrams like in Fig.1 where rays seem to be scattered from nothing!
Funda Check What does this mean?
Few points are to be noted in this context. The ray ‘picture’ is only valid in the realm of geometrical
optics, where the wave nature of light is not considered (& also the discrete nature of matter is
ignored; i.e. matter is treated like a continuum). In diffraction we are in the domain of physical optics.
The wave impinges on the entire volume of material including the plane of atoms (the effect of which
can be quantified using the atomic scattering power* and the density of atoms in the plane). Due to the
‘incoming’ wave the atomic dipoles are set into oscillation, which further act like emitter of waves
In Bragg’s viewpoint, the atomic planes are to be kept in focus and the wave (not just a ray) impinges
on the entire plane (some planes have atoms in contact and most have atoms, which are not in contact
along the plane see Fig.2).
Wave impinging on a crystal (parallel wave-front). (Note there are no ‘rays’. A vector drawn normal to the wave-front,
in the direction of propagation can be considered as the ray)
Fig.2
??
Fig.1
* To be considered later
A plane in Bragg’s viewpoint can be characterized by two factors: (a) atomic density (atoms/unit area on the plane), (b) atomic scattering
factor of the atoms.
More about the Bragg’s viewpoint
“It is difficult to give an explanation of the nature of the semi-transparent layers or planes
that is immediately convincing, as they are a concept rather than a physical reality.
Crystal structures, with their regularly repeating patterns, may be referred to a 3D grid and
the repeating unit of the grid, the unit cell, can be found. The grid may be divided up into
sets of planes in various orientations and it is these planes which are considered in the
derivation of Bragg’s law. In some cases, with simple crystal structures, the planes also
correspond to layers of atoms, but this is not generally the case. See Section 1.5 for further
information. [1]
Some of the assumptions upon which Bragg’s law is based may seem to be rather dubious.
For instance, it is known that diffraction occurs as a result of interaction between X-rays
and atoms. Further, the atoms do not reflect X-rays but scatter or diffract them in all
directions. Nevertheless, the highly simplified treatment that is used in deriving Bragg’s
law gives exactly the same answers as are obtained by a rigorous mathematical treatment.
We therefore happily use terms such as reflexion (often deliberately with this alternative,
but incorrect, spelling!) and bear in mind that we are fortunate to have such a simple and
picturesque, albeit inaccurate, way to describe what in reality is a very complicated
process.” [1]
[1] Anthony R West, Solid State Chemistry and its Applications, Second Edition, John Wiley & Sons Ltd., Chichester, 2014.
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?
Diffraction is a process in which
‘linear information’ (the d-spacing of the planes)
is converted to ‘angular information’ (the angle of diffraction, Bragg).
If the detector is placed ‘far away’ from the sample (i.e. ‘R’ in the figure below is large) the
distances along the arc of a circle (the detection circle) get amplified and hence we can make
‘easy’ measurements.
This also implies that in XRD we are concerned with angular resolution instead of linear
resolution.
Sharp peaks are obtained from crystalline materials (using parallel, monochromatic
radiation), while typically a broad peak is obtained from an amorphous material. The sharp
peak is referred to as a Bragg peak.
Defects (like point defects, thermal vibration, partial ordering) in the crystal can give rise to
low intensity scattering between the Bragg peaks. This is termed as diffuse scattering.
We had mentioned that Bragg’s equation is a negative statement: i.e. just because Bragg’s
equation is satisfied a ‘reflection’ may not be observed.
Let us consider the case of Cu K radiation ( = 1.54 Å) being diffracted from (100) planes
of Mo (BCC, a = 3.15 Å = d100).
1.54
2 d100 Sin100 Sin100 0.244 100 14.149 But this reflection is
2 d100 2(3.15) absent in BCC Mo
The missing reflection is due to the This ‘issue’ arises because so far we have talked
presence of additional atoms in the unit about (hkl) planes and nothing about atoms on
those planes or within the unit cell.
cell (which are positions at lattice
points) which we shall consider next. The wave scattered from the middle plane is out
of phase with the ones scattered from top and
bottom planes. I.e. if the green rays are in phase
(path difference of ) then the red ray will be
exactly out of phase with the green rays (path
difference of /2).
The scattering power of these two planes (the
green and the red) are identical, as both the
planes contain the same atom and have 1 atom
per a2 area.
Continuing with the case of BCC Mo…
However, the second order reflection from (100) planes (which is equivalent to the first order reflection
from the (200) planes) is observed.
2 1.54
Sin100 0.48 2nd order
100 ~ 1nd order
200 29.26
2 d100 3.15
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!
Note that (110)blue coloured planes existed before and after introducing an
atom at unit cell centre at (½, ½ ½)grey coloured. Thus lattice centering
does not lead to any waves being scattered out of phase.
Important
points
Lattice point
Intensity of the Scattered Waves
Bragg’s equation tells us about the position of the diffraction peaks (in terms of ) but
tells us nothing about the intensities. The intensities of the peaks depend on many factors as
considered here.
Scattering by a crystal can be understood in three steps
C
Unit cell (uc) Structure factor (F) Structure factor calculations
&
Click here to know more about Intensity in powder patterns
The concept of a Reciprocal lattice and the Ewald Sphere construction:
Reciprocal lattice and Ewald sphere constructions are important tools towards understanding
diffraction.
(especially diffraction in a Transmission Electron Microscope (TEM))
A lattice in which planes in the real lattice become points in the reciprocal lattice is a very
useful one in understanding diffraction.
Structure factor calculations give us the intensities which decorate the reciprocal lattice to
give us the reciprocal crystal.
click here & here to go to a detailed description of these topics.
Click here to know more about Reciprocal Lattice & Ewald Sphere construction
Selection / Extinction Rules Click here to see the derivations of selection rules: Structure factor calculations
As we have noted before even if Bragg’s equation is satisfied, ‘reflections may go missing’
this is due to the presence of additional atoms in the unit cell.
These atoms may be present at ‘additional’ lattice sites or as a part of the motif. In the case of DC crystal, in addition to the
restrictions/conditions imposed for the FCC lattice, further conditions/restrictions are imposed due to presence of atoms as a part of the motif.
The reflections present and the missing reflections due to additional atoms in the unit cell are
listed in the table below.
Bravais Lattice* Reflections which may be present Reflections necessarily absent
Simple All None
Body centred (h + k + l) even (h + k + l) odd
Face centred h, k and l unmixed (i.e. all even or all odd) h, k and l mixed
End centred (C centred) h and k unmixed (centering along ‘l’ index) h and k mixed
Continued…
FCC.
100. Fig.1. On introducing face centering lattice positions, a new orange plane is created exactly midway between
the green and the blue planes. The atomic density of all these planes are 2 atoms per a 2. Missing.
110. Fig.2. When we introduce face centring atoms (orange colour), some of these sit on the original (110) planes
(grey lines in projection), while new planes (orange lines in projection) also created, which are midway
between the grey planes. The atomic density of the grey planes are 2 atoms per a 22 area. The area of the
orange planes are 1 atom per a22/2 area (i.e. identical to the grey planes). Missing.
111. Fig.3. When we introduce atoms at face centres, these lie on pre-existing planes (the blue and green planes);
hence, the 111 reflection will be present in FCC crystals. Present.
200. Fig.4. The 200 reflection is the 2 reflection from the 100 planes. This implies that the path difference between
the grey planes is one and hence this will be present. Present.
Fig.1 (100)
Fig.2 (110)
Fig.3 (111) Grey plane has
2 atoms
a2 2
Orange plane has Fig.4 (200)
1atoms 2 atoms
a2 2
2
2 a 2 Continued…
DC.
For DC we can start with the selection rules for FCC and further work out the effect of an additional atom, which is part
of the motif. This implies that 100 and 110 reflections will be missing.
100. Missing as per the rules of the FCC lattice. Missing.
110. Missing as per the rules of the FCC lattice. Missing.
200. This reflection is present in the FCC lattice, but now we have to consider the effect of the additional atoms,
which are part of the motif. The grey planes scatter in phase (the 200 planes). On the introduction of orange
atoms at (¼. ¼, ¼) and equivalent positions a new plane has to be drawn. This plane will scatter exactly out of
phase (/2) with the grey planes and hence the 200 reflection will be missing in the DC structure. Missing.
The broad process followed to ‘go from’ a cubic crystal to get lattice parameters is as below.
Laue λ variable
Panchromatic X-rays Single Technique θ fixed
dhkl Cubic a
2 d Sin (1) Cubic crystal (2)
h2 k 2 l 2
(2) in (1)
4 a 2
sin 2
4a 2
2 2 2
2
(h 2 k 2 l 2 ) sin 2
h k l 2
2
a2 (h 2 k 2 l 2 ) (h 2 k 2 l 2 ) sin 2
4 sin 2
SC 1 2 3 4 5 6 8 …
BCC 1 2 3 4 5 6 7 …
FCC 3 4 8 11 12 …
DC 3 8 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!
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) Usually the source is
fixed and the
detector and sample
Different cones are rotated
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
In the power diffraction method a 2 versus intensity (I) plot is obtained from the
diffractometer (and associated instrumentation).
The ‘intensity’ is the area under the peak in such a plot (NOT the height of the peak).
The information of importance obtained from such a pattern is the ‘relative intensities*’
and the absolute value of the intensities is of little importance (the longer we irradiate the sample the more will be
the intensity under the peak) (for now).
A table is prepared as below to tabulate the data and make calculations to find the crystal
structure (restricting ourselves to cubic crystals for the present).
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)
Peaks are all not of same intensity
No brackets are used around the indexed numbers
(the peaks correspond to planes in the real space)
Note:
Peaks or not idealized peaks broadened.
111
Increasing splitting of peaks with g .
Peaks are all not of same intensity.
There is a ‘noisy’ background.
Here the background is subtracted
(else we may have a varying background).
200
220
311
222
400
In low angle peaks K1 & K2 peaks merged K1 & K2 peaks resolved in high angle peaks
(in 222 and 400 peaks this can be seen)
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.
Peaks could be shifted from their ideal positions
Note peak splitting has not been
Could be due to uniform strain→ macrostrain. included here as this comes from
‘symmetry lowering’ (i.e. crystal with
Relative intensities of the peaks could be altered lower symmetry)
Could be due to texture in the sample.
Funda Check What is the maximum value of possible (experimentally)? Ans: 90
1) smaller the wavelength of the X-rays, more will be the number of peaks possible.
From Bragg’s equation: [=2dSin], (Sin)max will correspond to dmin. (Sin)max=1.
Hence, dmin=/2. Hence, if is small then planes with smaller d spacing (i.e. those which
occur at higher 2 values) will also show up in a XRD patter (powder pattern). Given that
experimentally cannot be greater than 90.
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 2d min d min
Sin max 2
Solved example
Determination of Crystal Structure (lattice type) from 2 versus Intensity Data
1
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).
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
2
Another example
Given the positions of the Bragg peaks we find the lattice type
FCC lattice
Comparison of diffraction patterns of SC, BCC & B2 structures
Click here
More Solved
Examples on XRD Click here
Funda Check What happens when we increase or decrease ?
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 as obtaining monochormatic x-rays with any arbitrary wavelength and
good intensity is ‘difficult’!!)
And More….
Determine if the material is amorphous or crystalline Schematics
Crystal
Intensity →
Sharp peaks
0 90 180
Diffraction angle (2) →
Monoatomic gas
Intensity →
No peak
Intensity →
0 90 180
Diffuse Peak
Diffraction angle (2) →
Continued…
0 90 180
Amorphous solid
Actual diffraction pattern
from an amorphous solid
Intensity (a.u.)
20 30 40 50 60 70
2θ ( )
a
d13 a a
10 d34
25 5
The number of peaks we obtain in a powder
diffraction pattern depends on the wavelength
With increasing indices the
interplanar spacing decreases of x-ray we are using. Planes with ‘d’ < /2 are
not captured in the diffraction pattern.
a
d10 a These peaks with small ‘d’ occur at high angles
1
in diffraction pattern.
a
a d11
d12 2
5
Q&A How to increase the number of peaks in a XRD pattern?
We have noted that (e.g. for DC crystal) the number of available peaks in the 2 regime
could be insufficient for a given analysis.
The number of peaks can be increased in two ways:
1) using Mo Kα instead of Cu Kα,
2) first obtain pattern with β filter and then remove the filter to get more lines.
Target Of K
Metal radiation (Å)
200
Mo 0.71
Cu 1.54
Cr K, = 2.29 Å 2θ Co 1.79
Fe 1.94
40 50 60 70 80 90 100 110 120 Cr 2.29
Q&A In early parts of the chapter, we had noted that we have many sources of nearly
monochromatic X-rays are available. Why are so many radiation sources needed?
There are two main reasons why we need some options at our disposal.
1) Some sources ‘fluoresce’ with in conjunction with some elements in the material (e.g. Co
fluoresces with Cu K). This inelastic process gives rise to an increased background and
hence a lower signal to background ratio. In the case of Co in the sample, Cr K radiation can
be used.
2) Smaller wavelengths of radiation give rise to more peaks in a powder XRD pattern. Cu K
gives more peaks as compared to Cr K radiation. (The point we saw previously).
Cr K, = 2.29 Å 2θ
2
| k |
n 2d Sin( )
4
2dn Sin( ) | G | q 2 k Sin( ) Sin( )
1 Sin( )
2
dn
End
Diffuse peak from
Cu-Zr-Ni-Al-Si
Metallic glass