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You are on page 1of 52

MATERIALS SCIENCE

Part of & A Learners Guide

X- Ray Sources ENGINEERING

AN INTRODUCTORY E-BOOK

Diffraction: Braggs Law Anandh Subramaniam & Kantesh Balani

Materials Science and Engineering (MSE)

Indian Institute of Technology, Kanpur- 208016

Email: anandh@iitk.ac.in, URL: home.iitk.ac.in/~anandh

http://home.iitk.ac.in/~anandh/E-book.htm

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

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?

Braggs 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

line_broadening.ppt

other_signals_xray.ppt

reciprocal_lattice.ppt

structure_factor_calculations.ppt

Understanding_diffraction.ppt

XRD_lattice_parameter_calculation.ppt

XRD_powder_diffraction.ppt

XRD_sample_patterns.ppt

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.

Click here to know more about this

** 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.

Target

Mo Target impacted by electrons accelerated by a 35 kV potential shows the emission

spectrum as in the figure below (schematic)

K monochromatic doing XRD studies

Target Of K

White K Metal radiation ()

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

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

X-ray sources with different for doing XRD studies

radiation radiation () radiation () (mm)

()

0.0461

Mo 20 0.7093 0.71359 0.63229 Zr

0.0678

Cu 8.98 1.540598 1.54439 1.39222 Ni

0.017

Ni 8.33 1.65791 1.66175 1.50014 Co

0.0158

Co 7.71 1.78897 1.79285 1.62079 Fe

0.0166

Fe 7.11 1.93604 1.93998 1.75661 Mn

0.0168

Cr 5.99 2.2897 2.29361 2.08487 V

0.169

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 hit a specimen, the interaction can

result in various signals/emissions/effects.

The coherently scattered X-rays are the ones Incident X-rays

important from a XRD perspective.

Fluorescent X-rays

Electrons

Scattered X-rays

Compton recoil Photoelectrons

From bound charges From loosely bound charges

Transmitted beam

X-rays can also be refracted (refractive index slightly less than 1) and reflected (at very small angles)

Diffraction Click here to Understand 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).

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)

Aspects related to the wave

Diffraction pattern

Aspects related to the material Crystalline*,**

with sharp peaks

Aspects related to the diffraction set-up

(diffraction geometry) Fraunhofer geometry

[1] The intensity- plot looks like a function (in an ideal situation).

* A quasicrystalline array will also lead to diffraction with sharp peaks (which we shall not consider in this text).

** Amorphous material will give broadened (diffuse) peak (additional factors related to the sample can also give a diffuse peak).

Some comments and notes

electromagnetic waves (light, X-rays),

matter waves** (electrons, neutrons) or

mechanical waves (sound, waves on water surface).

Not all objects act like scatterers for all kinds of radiation.

If wavelength is not of the order of the spacing of the scatterers, then the number

of peaks obtained may be highly restricted (i.e. we may even not even get a

single diffraction peak!).

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 (large number) is categorized under diffraction.

Fraunhofer diffraction geometry implies that parallel waves are impinging on the

scatterers (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

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

the incoming x-rays

Schematics

Sets Electron cloud into oscillation

Small effect neglected

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.

Incident and scattered

waves are in phase if

Scattering from across planes is in phase A Laue diffraction pattern

with sharp peaks.

*Max von Laues postulate: If (i) crystals have a periodic arrangement of atoms and if (ii)

x-rays of waves (concepts which were not confirmed till ), 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

Click here to know more and get

introduced to Laue equations describing

diffraction

These can be in phase if

Extra path traveled by scattered waves XB incident = scattered

A B

and NOT reflection

X Y

BRAGGs EQUATION

Warning: we are using ray diagrams in spite of

being in the realm of physical optics Let us consider scattering across planes

constructive and

destructive interference

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 Braggs 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. How

come these rays go missing?

destructive interference of

just of-Bragg rays occur

Which remains same

Note that they almost constructively interfere! thereafter (like in the

BB plane)

Funda Check How to see that path difference increases with angle?

Laue versus Bragg*

In Laues picture constructive and destructive interference at various points in space is

computed using path differences (and hence phase differences) given a crystalline array of

scatterers.

Bragg simplified this picture by considering this process as reflections from atomic planes.

(More about the Braggs viewpoint soon). Click here to know more about the Laue Picture

*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 Braggs as I have done in this chapter)

[1]

discover new ways of thinking about them. William Lawrence Bragg.

[1] http://www.nobelprize.org/nobel_prizes/physics/laureates/1915/index.html

Reflection versus Diffraction

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 Diffraction

Occurs throughout the bulk

Occurs from surface (though often the penetration of x-rays in only of the

order of 10s of microns in a material)

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 Braggs 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:

(i.e. how many wavelengths of the X-ray go on to make the path difference between planes). Note:

Note: if hkl reflection (corresponding to n=1) occurs at hkl then 2h 2k 2l reflection (n=2) will occur at a higher angle 2h 2k 2l.

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.

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.

Order of the reflection (n)

For Cu K radiation ( = 1.54 ) and d110= 2.22

n Sin = n/2d

Second order reflection from (110) planes 110

2 0.69 43.92

Also considered as first order reflection from (220) planes 220

a

d Cubic crystal

hkl e.g.

h2 k 2 l 2 a d 220 1

a

d 220

d nh nk nl 8 d110 2

(nh) 2 ( nk ) 2 ( nl ) 2

a

a d

d110 d 220

d110

dnh nk nl hkl 2 2

n h2 k 2 l 2 n

In XRD nth order reflection from (h k l) is considered as 1st order reflection from (nh nk nl)

n 2dhkl sin hkl

d nh nk nl 1

d hkl

2 sin d hkl n d 200 1

n d100 2

2dnh nk nl sin nh nk nl

All these form the (200) set

Hence, (100) planes are a subset of (200) planes

d300 1

d100 3

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).

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 Braggs 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) Fig.2

(note there are no rays)

??

Fig.1

* To be considered later

A plane in Braggs 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 Braggs viewpoint

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 Braggs 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.

Some of the assumptions upon which Braggs 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 Braggs 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?

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.

diffraction this angle of deviation

(2) is plotted instead of .

Forward and Back Diffraction

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

What is (theta) in the Braggs equation?

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.

Usually, in this context implies Bragg (i.e. the angle at which Braggs equation is

satisfied).

It is NOT the angle between the x-rays and the sample surface (note: specimens could be

spherical or could have a rough surface).

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).

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 presence of additional atoms in the unit cell

(which are positions at lattice points) which we shall consider next.

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).

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!

Funda Check

Note that (110)blue coloured planes existed before and after introducing an

atom at unit cell centre at (, )grey coloured. Thus lattice centering

does not lead to any waves being scattered out of phase.

Important

points

at lattice points (as we may chose a non-primitive unit cell)

or as a part of the motif

can alter the intensities of some of the reflections

Some of the reflections may even go missing

The Intensities tells us about the motif.

Intensity of the Scattered Waves

Braggs 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

A intensity of reflections (and why some reflections go

missing), three levels of scattering have to be considered:

Electron Polarization factor 1) scattering from electrons

2) scattering from an atom

3) scattering from a unit cell

Click here to know the details

B Structure Factor (F): The resultant wave scattered

by all atoms of the unit cell

Atom Atomic scattering factor (f) 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

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

As we have noted before even if Braggs equation is satisfied, reflections may go missing

this is due to the presence of additional atoms in the unit cell.

The reflections present and the missing reflections due to additional atoms in the unit cell are

listed in the table below. Click here to see the derivations

Structure factor calculations

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

SC All

BCC (h + k + l) even

FCC h, k and l unmixed

Either, h, k and l are all odd or

DC

all are even & (h + k + l) divisible by 4

h2 + k2 + l2 SC FCC BCC DC

Allowed reflections in

1 100

SC*, FCC*, BCC* &

2 110 110

DC crystals

3 111 111 111

4 200 200 200

5 210

6 211 211

7

8 220 220 220 220

Cannot be expressed as (h2+k2+l2) 9 300, 221

10 310 310

11 311 311 311

12 222 222 222

13 320

14 321 321

15

16 400 400 400 400

17 410, 322

* lattice decorated with 18 411, 330 411, 330

monoatomic/monoionic motif

19 331 331 331

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.

Monochromatic X-rays Powder specimen METHOD variable

LAUE variable

Panchromatic X-rays Single

TECHNIQUE fixed

ROTATING fixed

Varied by rotation CRYSTAL

Monochromatic X-rays rotated

METHOD

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

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

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

How to visualize the occurrence of peaks at various angles

It is somewhat difficult to actually visualize a random assembly of crystallites giving peaks at various angels in a XRD

scan. The figures below are expected to give a visual feel for the same. [Hypothetical crystal with a = 4 is assumed with

=1.54. Only planes of the type xx0 (like (100,110)are considered].

For convenience the source

may be stationary (and the

sample and detector may

rotate but the effect is

equivalent)

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 d Sin()

2 110 2.83 0.27 15.80

3 111 2.31 0.33 19.48

4 200 2.00 0.39 22.64

5 210 1.79 0.43 25.50

6 211 1.63 0.47 28.13

8 220 1.41 0.54 32.99

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 (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 in the next slide to tabulate the data and make calculations to find the

crystal structure (restricting ourselves to cubic crystals for the present).

the intensity of the strongest peak. Powder diffraction pattern from Al

[Energy/area/time] but here it

is plotted as arbitrary units.

Increasing d This is peak (sometimes called a

line- a hangover from Debye

Scherrer camera usage)

Determination of Crystal Structure (lattice type) 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 (empty starting table of columns is shown below- completed table shown later).

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

space (these are not planes they

correspond to panes in real space)

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)

around the indices!

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

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.

micro-strain (e.g. due to dislocations will lead

Peak Broadening Small crystallite size to peak broadening)

Crystal defects (bent planes) Click here to know more

fields associated with these defects

direction to the incident ray.

Beyond this angle, it is as if the source and

detector positions are switched.

2max is 180.

Funda Check What will determine how many peaks I will get?

1) smaller the wavelength of the X-rays, more will be the number of peaks possible.

From Braggs 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)

1 38.52 19.26 0.33 0.11 3 111 2.34

2 44.76 22.38 0.38 0.14 4 200 2.03

3 65.14 32.57 0.54 0.29 8 220 1.43

4 78.26 39.13 0.63 0.40 11 311 1.22

5 82.47 41.235 0.66 0.43 12 222 1.17

6 99.11 49.555 0.76 0.58 16 400 1.01

7 112.03 56.015 0.83 0.69 19 331 0.93

8 116.60 58.3 0.85 0.72 20 420 0.91

9 137.47 68.735 0.93 0.87 24 422 0.83

10 163.78 81.89 0.99 0.98 27 333 0.78

From the ratios in column 6 we conclude that FCC Note

(h 2 k 2 l 2 ) sin 2

a

Using 2 d Sin 1.54 2 d111 Sin111 2 0.33

o

3

a 4.04 A Al 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

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

Ratios

2 Sin Sin2 number

of Sin2 0.134/3 = 0.044667 ratios

1 21.5 0.366 0.134 1 3

2 25 0.422 0.178 1.33 3.99 4

3 37 0.60 0.362 2.70 8.10 8

4 45 0.707 0.500 3.73 11.19 11

5 47 0.731 0.535 4 11.98 12

6 58 0.848 0.719 5.37 16.10 16

7 68 0.927 0.859 6.41 19.23 19

FCC

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!!)

hkl d Sin() 2 Sin() 2 Sin() 2

111 2.34 0.33 19.26 38.52 0.64 39.87 79.74 0.02 1.22 2.45

200 2.03 0.38 22.38 44.76 0.74 47.64 95.28 0.02 1.41 2.82

220 1.43 0.54 32.57 65.14 1.05 - - 0.03 2.00 4.01

311 1.22 0.63 39.13 78.26 1.23 - - 0.04 2.35 4.70

222 1.17 0.66 41.24 82.47 1.28 - - 0.04 2.45 4.90

400 1.01 0.76 49.56 99.11 1.49 - - 0.05 2.84 5.68

331 0.93 0.83 56.02 112.03 1.61 - - 0.05 3.08 6.16

420 0.91 0.85 58.30 116.60 1.65 - - 0.05 3.15 6.30

422 0.83 0.93 68.74 137.47 1.81 - - 0.06 3.45 6.91

333 0.78 0.99 81.89 163.78 1.92 - - 0.06 3.68 7.35

With CuK = 1.54 few peaks all the peaks get

crowded to small

angles

And the detector may not be able to resolve

these peaks if they come too close!

Applications of XRD

We have already seen these applications

Lattice parameter determination

And More.

Intensity Crystal Schematics

the diffraction patterns of various phases

Sharp peaks

0 90 180

Diffraction angle (2)

Monoatomic gas

Intensity

No peak

Intensity

0 90 180

Diffuse Peak

0 90 180

Amorphous solid

Diffuse peak from Actual diffraction

Cu-Zr-Ni-Al-Si pattern from an

Metallic glass amorphous solid

A amorphous solid which shows glass transition in a Differential Scanning Calorimetry (DSC)

plot is also called a glass. In general usage a glass may be considered equivalent to a

amorphous solid (at least loosely in the structural sense).

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 What is the minimum spacing between planes possible in a crystal?

How many diffraction peaks can we get from a powder pattern?

dhkl a

h2 k 2 l 2

As h,k, l increases, d decreases we could have planes with infinitesimal spacing

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 K instead of Cu K

2) first obtain pattern with filter and then remove the filter to get more lines.

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