X-RAY DIFFRACTION

X- Ray Sources Diffraction: Braggs Law Crystal Structure Determination Elements of X-Ray Diffraction
B.D. Cullity & S.R. Stock Prentice Hall, Upper Saddle River (2001)

Recommended websites:
http://www.matter.org.uk/diffraction/ http://www.ngsir.netfirms.com/englishhtm/Diffraction.htm

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? Braggs equation What determines the position of the XRD peaks? Ans) the lattice What determines the intensity of the XRD peaks? Ans) the motif 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) should be of the same order as the wavelength In crystals the typical interatomic spacing ~ 2-3 so the suitable radiation is X-rays Hence, X-rays can be used for the study of crystal structures

Generation of X-rays
X-rays can be generated by decelerating electrons

Beam of electrons

Target

X-rays

A accelerating (or decelerating) charge radiates electromagnetic radiation

Mo Target impacted by electrons accelerated by a 35 kV potential shows the emission spectrum as in the figure below (schematic)

K
Intensity
White radiation

Intense peak, nearly monochromatic

Characteristic radiation due to energy transitions in the atom

0.2

0.6

1.0

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

Available X-ray sources with different for doing XRD studies

Target Metal Mo Cu Co Fe Cr

Of K radiation () 0.71 1.54 1.79 1.94 2.29

 When X-rays hit a specimen, the interaction can result in various signals/emissions/effects The coherently scattered X-rays are the ones important from a XRD perspective

Incident X-rays

SPECIMEN

Heat

Fluorescent X-rays Scattered X-rays

Electrons
Compton recoil Photoelectrons

Coherent Incoherent (Compton modified) From bound charges From loosely bound charges
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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 X-ray diffraction (XRD) Diffraction (with XRD being a specific case) requires two important conditions to be met: Coherent waves (with wavelength ) on a Crystalline array* with spacing of the order of (~) The waves could be electromagnetic waves (light, X-rays), matter waves** (electrons, neutrons) or mechanical waves (sound, waves on water surface) In short diffraction is coherent reinforced scattering (or reinforced scattering of coherent waves) In a sense diffraction is nothing but a special case of constructive (& destructive) interference
To give an analogy the results of Youngs double slit experiment is interpreted as interference, while the result of multiple slits is categorized under diffraction

* A quasicrystalline array will also lead to diffraction (which we shall not consider in this text) ** With a de Broglie wavelength

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

Incoming X-rays

Secondary emission

Schematically

Schematically

Sets Electron cloud into oscillation

Sets nucleus into oscillation Small effect neglected

Schematically

Oscillating charge re-radiates In phase with the incoming x-rays

Some points to recon with

We can get a better physical picture of diffraction by using Laues formalism (leading to the Laues equations) However, a parallel approach to diffraction is via the method of Bragg, wherein diffraction can be visualized as reflections from a set of planes As the approach of Bragg is easier to grasp we shall use that in this elementary text We shall do some intriguing mental experiments to utilize the Braggs equation (Braggs model) with caution

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

In plane scattering is in phase Incident and scattered waves are in phase if Scattering from across planes is in phase

Let us consider in-plane scattering

A B

Atomic Planes

There is more to this Click here to know more and get introduced to Laue equations describing diffraction

Extra path traveled by incoming waves AY Extra path traveled by scattered waves XB

These can be in phase if incident = scattered

A B

But this is still reinforced scattering and NOT reflection

Y

BRAGGs EQUATION

Let us consider scattering across planes

Deviation = 2

Ray 1

Ray 2

dS in

Click here to visualize constructive and destructive interference

The path difference between ray 1 and ray 2 = 2d Sin For constructive interference: n = 2d Sin the Braggs equation

Reflection versus Scattering

Though diffraction (according to Braggs picture) has been visualized as a reflection from a set of planes with interplanar spacing d diffraction should not be confused with reflection (specular reflection) Reflection Occurs from surface Takes place at any angle ~100 % of the intensity may be reflected Diffraction Occurs throughout the bulk Takes place only at Bragg angles Small fraction of intensity is diffracted

Note: X-rays can be reflected at very small angles of incidence

Understanding the Braggs equation

n = 2d Sin The equation is written better with some descriptive subscripts:

n Cu K = 2 d hkl Sin hkl

n is an integer and is the order of the reflection
(i.e. how many wavelengths of the X-ray go on to make the path difference between planes)

Braggs equation is a negative statement

If Braggs eq. is NOT satisfied NO reflection can occur If Braggs eq. is satisfied reflection MAY occur (How?- we shall see this a little later)

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

Order of the reflection (n)

For Cu K radiation ( = 1.54 ) and d110= 2.22
n 1 2 Sin = n/2d 0.34 0.69 20.7 First order reflection from (110) 110 43.92 Second order reflection from (110) planes 110 Also considered as first order reflection from (220) planes 220

Relation between dnh nk nl and dhkl

d hkl =
d nh nk nl =

a h2 + k 2 + l 2
a (nh)2 + ( nk ) 2 + (nl ) 2

e.g.

d nh nk nl =

a n h2 + k 2 + l 2

d hkl n

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
d nh nk nl d hkl 1 = n
Hence, (100) planes are a subset of (200) planes

= 2d nh nk nl sin

d 200 1 = d100 2

d300 1 = d100 3

Important point to note: In a simple cubic crystal, 100, 200, 300 are all allowed reflections. But, there are no atoms in the planes lying within the unit cell! Though, first order reflection from 200 planes is equivalent (mathematically) to the second order reflection from 100 planes; for visualization purposes of scattering, this is better thought of as the later process (i.e. second order reflection from (100) planes)

Forward and Back Diffraction

Here a guide for quick visualization of forward and backward scattering (diffraction) is presented

The missing reflections

We had mentioned that Braggs equation is a negative statement: i.e. just because Braggs equation is satisfied a reflection may not be observed Let us consider the case of Cu K radiation ( = 1.54 ) being diffracted from (100) planes of Mo (BCC, a = 3.15 = d100)

= 2 d100 Sin100

Sin100

1.54 = = = 0.244 2 d100 2(3.15)

100 = 14.149

But this reflection is absent in BCC Mo

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

1 nd order 200

= 29.267

Important point

Presence of additional atoms/ions/molecules in the UC at lattice points or as a part of the motif can alter the intensities of some of the reflections

Intensity of the Scattered electrons

Scattering by a crystal can be understood in three steps To understand the scattering from a crystal leading to the intensity of reflections (and why some reflections go missing), three levels of scattering have to be considered: 1) scattering from electrons 2) scattering from an atom 3) scattering from a unit cell Click here to know the details

A
Electron Polarization factor

Atom Atomic scattering factor (f)

Structure Factor (F): The resultant wave scattered by all atoms of the unit cell The Structure Factor is independent of the shape and size of the unit cell; but is dependent on the position of the atoms/ions etc. within the cell

Unit cell (uc) Structure factor (F)

Structure factor calculations

The concept of a reciprocal lattice and the Ewald Sphere construction: a lattice in which planes in the real lattice become points in the reciprocal lattice is a very useful one in understanding diffraction click here to go to a detailed description of these topics

Selection / Extinction Rules

The reflections present and the missing reflections due to additional atoms in the unit cell Bravais Lattice Simple Body centred Face centred End centred Reflections which may be present all (h + k + l) even h, k and l unmixed h and k unmixed C centred Bravais Lattice SC BCC FCC DC Reflections necessarily absent None (h + k + l) odd h, k and l mixed h and k mixed C centred Allowed Reflections All (h + k + l) even h, k and l unmixed h, k and l are all odd Or all are even & (h + k + l) divisible by 4

h2 + k2 + l2 1

SC 100 110 111 200 210 211

FCC

BCC

DC

Allowed reflections in SC*, FCC*, BCC* & DC crystals

2 3 4 5 6 7 8 9 10 11 12 13

110 111 200 200 111

211

220 300, 221 310 311 222 320 321

220

220

220

310 311 222 222 311

* lattice decorated with monoatomic/monoionic motif

14

321

The ratio of (h2 + k2 + l2) derived from extinction rules

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 DC

1 1 3 3

2 2 4 8

3 3 8 11

4 4 11 16

5 5 12

6 6

8 7

Crystal structure determination

As diffraction occurs only at specific Bragg angles, the chance that a reflection is observed when a crystal is irradiated with monochromatic X-rays at a particular angle is small (added to this the diffracted intensity is a small fraction of the beam used for irradiation) The probability to get a diffracted beam (with sufficient intensity) is increased by either varying the wavelength () or having many orientations (rotating the crystal or having multiple crystallites in many orientations)
The three methods used to achieve high probability of diffraction are shown below Many s (orientations) Powder specimen Single

Monochromatic X-rays

POWDER METHOD LAUE TECHNIQUE ROTATING CRYSTAL METHOD

fixed variable variable fixed fixed rotated

Panchromatic X-rays

Monochromatic X-rays

Varied by rotation

Only the powder method (which is commonly used in materials science) will be considered in the text

THE POWDER METHOD

In the powder method the specimen has crystallites (or grains) in many orientations (usually random) Monochromatic* X-rays are irradiated on the specimen and the intensity of the diffracted beams is measured as a function of the diffracted angle In this elementary text we shall consider cubic crystals

= 2 d Sin
(2) in (1)

(1)

Cubic crystal

d Cubic =

a h2 + k 2 + l 2

(2)

4a 2 sin 2 2 = 2 h + k2 + l2

4a 2 (h 2 + k 2 + l 2 ) = 2 sin 2

2 a2 = (h 2 + k 2 + l 2 ) 4 sin 2
* In reality this is true only to an extent

(h 2 + k 2 + l 2 ) sin 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
Different cones for different reflections

Determination of Crystal Structure from 2 versus Intensity Data in Powder Method 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 A table is prepared as in the next slide to tabulate the data and make calculations to find the crystal structure (restricting ourselves to cubic crystals for the present)

Powder diffraction pattern from Al Radiation: Cu K, = 1.54

Determination of Crystal Structure from 2 versus Intensity Data

The following table is made from the 2 versus Intensity data (obtained from a XRD experiment on a powder sample

Intensity

Sin

Sin2

ratio

Powder diffraction pattern from Al

Radiation: Cu K, = 1.54

Note: Peaks or not idealized peaks broadened Increasing splitting of peaks with g Peaks are all not of same intensity

111 200

220

311 222

1 & 2 peaks resolved

400

Powder diffraction pattern from Al

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)

Peaks are all not of same intensity

Determination of Crystal Structure from 2 versus Intensity Data

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) n 1 2 3 4 5 6 7 8 9 2 38.52 44.76 65.14 78.26 82.47 99.11 112.03 116.60 137.47 19.26 22.38 32.57 39.13 41.235 49.555 56.015 58.3 68.735 Sin 0.33 0.38 0.54 0.63 0.66 0.76 0.83 0.85 0.93 Sin2 0.11 0.14 0.29 0.40 0.43 0.58 0.69 0.72 0.87 ratio 3 4 8 11 12 16 19 20 24 Index 111 200 220 311 222 400 331 420 422

Solved example

From the ratios in column 6 we conclude that

FCC

Using = 2 d Sin
a = 4.04 A Al
o

1.54 = 2 d111 Sin111 = 2

a 0.33 3

We can get the lattice parameter which correspond to that for Al

Note: Error in d spacing decreases with so we should use high angle lines for lattice parameter calculation

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Solved example

Another example Given the positions of the Bragg peaks we find the lattice type

2 1 2 3 4 5 6 7 21.5 25 37 45 47 58 68

Sin 0.366 0.422 0.60 0.707 0.731 0.848 0.927

Sin2 0.134 0.178 0.362 0.500 0.535 0.719 0.859

ratio 3 4 8 11 12 16 19

FCC

More Solved Examples on XRDClick

Applications of XRD
Bravais lattice determination Lattice parameter determination Determination of solvus line in phase diagrams Long range order Crystallite size and Strain
Click here to know more Next slide

We have already seen these applications

Determine if the material is amorphous or crystalline

Intensity

Crystal
Schematic of difference between the diffraction patterns of various phases
Sharp peaks

Diffraction angle (2)

No peak

90

180 Monoatomic gas

Intensity

Diffraction angle (2) Intensity

Liquid / Amorphous solid 0

Diffraction angle (2)

90
Diffuse Peak

90

180