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X-RAY DIFFRACTION AND ELECTRON MICROSCOPY

(PCMT 4401)

B. Tech 7th Semester

Compiled By:

1. Dr.Prafulla Kumar Mallik


2. Mr. Amulyabihari Pattnaik

Department of Metallurgical and Material Engineering,


Indira Gandhi Institute of Technology (IGIT), Sarang,
Dhenkanal 759146, Odisha, India.
Disclaimer
This document does not claim any originality and cannot be used as a substitute for

prescribed textbooks. The information presented here is merely a collection by the committee

faculty members for their respective teaching assignments as an additional tool for the

teaching-learning process. Various sources as mentioned at the reference of the document as

well as freely available material from internet were consulted for preparing this document.

The ownership of the information lies with the respective authors or institutions. Further, this

document is not intended to be used for commercial purpose and the committee faculty

members are not accountable for any issues, legal or otherwise, arising out of use of this

document. The committee faculty members make no representations or warranties with

respect to the accuracy or completeness of the contents of this document and specifically

disclaim any implied warranties of merchantability or fitness for a particular purpose


Courses of Study
Subject: X-Ray and Electron Microscopy (3-0-0) Credits: 03

Module I (12 Hours)

Introduction to x-ray and properties of x-ray: Continuous characteristics x-ray, absorption,


filter, production and detection of x-rays. Diffraction of x-rays; special topics on
crystallography, directions and intensities of diffracted beams.

Module II (14 Hours)

Experimental methods in x-ray analysis; Laue methods, powder photographs diffractometer


and spectrometer measurements. Applications: orientation of single crystal, crystal structures
of polycrystalline materials, precise lattice parameter measurements.Calculation of integrated
intensity, structure factor calculation.
Application: Phase diagram, order-disorder transformation, chemical analysis, residual stress,
texture.

Module III (12 Hours)

Electron optical methods: (a) Scanning electron microscopy and X-ray microanalysis
including electron probe microanalysis, electron optics, and electron beam specimen
interaction, image formation in the SEM. X-ray spectral measurements: WDS and EDS,
quantitative X-ray analysis.

(b) Analytical transmission electron microscopy: Electron diffraction, reciprocal lattice,


analysis of SAD patterns; different electron diffraction techniques, atomic resolution
microscopy, analytical devices with TEM, field ion microscopy, scanning tunneling
microscopy, advanced techniques.

Books for reference:


1. Elements of X-Ray Diffraction by B. D. Cullity, Adison-Wesley.
2. Transmission Electron Microscopy by Williams, D.B. and Barry Carter C., Plenum
Press.
3. Scanning Electron Microscopy and X-Ray Microanalysis, by J.I. Goldstein, C. E.
Lyman
Suggested books of references
4. Structure of Metals by C. Barret and T. B. Massalski, Pergamon.
5. X-ray Diffraction its Theory and Applications by S. K. Chatterjee, Prentice Hall of
India.
6. Materials Characterization, Metals Handbook, Vol. 10, ASM
7. Characterization of Materials, by E N Kaufman, Wiley Publishers.
8. Lecture notes on NPTEL
Lesson Plan
Module I: Diffraction Techniques
Lecture 1: Review of Microstructure; Crystalline and Amorphous Materials;
Lecture 2: Overview of Techniques of Materials Characterization
Lecture 3: Generation of X-ray
Lecture 4: Properties and Characteristics of X-ray
Lecture 5:X-ray absorption
Lecture 6:X-ray Filters
Lecture 6: Braggs Law, X-ray Diffraction (XRD)
Lecture 7: Techniques of XRD
Lecture 8:X-ray Measurement Techniques
Lecture 9: Indexing of powder diffraction patterns
Module II: X-ray Analysis and Applications
Lecture 10:Scattering Phenomena by electron, atom and unit cell
Lecture 11:Structure factor calculation with single or multi atom basis
Lecture 12: Factors affecting XRD intensity
Lecture 13: XRD intensity calculation
Lecture 14: Crystal size determination
Lecture 15: Measurements of residual stress
Lecture 16: Texture studies using X-rays
Lecture 17: Phase diagram determination
Lecture 18: Supper lattice structure determination
Module III: Electron microscopy and Composition Analysis Techniques
Lecture 19: Electron and Neutron Diffraction
Lecture 20: Principles of Optical and Electron Microscopy
Lecture 21: Instrumentation of SEM
Lecture 22: Image formation techniques in SEM
Lecture 23: Interaction of electron beam with matters
Lecture 24: Microanalysis in Electron Microscopy (EDS, and WDS)
Lecture 25: Instrumentation of Transmission Electron Microscopy (TEM)
Lecture 26: Image formation techniques in TEM
Lecture 27: Indexing of diffraction pattern
Lecture 28: Principles of Scanning Probe Microscopy (AFM and STM)
Lecture 29: Principles of Scanning Probe Microscopy (AFM and STM)
Introduction
The course divided into three modules and in first and second module talks about the X-ray
diffractionin detail and third module talks about the TEM and SEM (Scanning Electron
Microscopy) characterisation techniques in briefly.

X-ray diffraction (XRD)

XRD is a technique for determining the structure (atomic and molecular) of materials. It
makes use of a photon source from characteristics radiation of atoms. It is widely used for
structural and phase identification of materials.
Scanning Electron Microscopy (SEM)
An SEM uses a beam of electrons to form the image using electromagnetic lens. But the
electrons used here are backscattered or secondary electrons. The beam is scanned or rastered
on the sample and the image is formed. The advantage of SEM over TEM is that need not
hard rule for the sample preparation and its widely used for microstructural characterisation
materials
Transmission Electron Microscopy (TEM)
In TEM, a beam of electrons is used to form an image of the transparent specimen having
thickness <100nm. That means the beam should be able to pass through the material of
interest so that sample preparation is an important step in TEM.

X-ray diffraction
The first technique we will focus on is XRD (X-ray diffraction). Other common name is X-
ray crystallography. X-rays were discovered by Wilhelm Rontgen in 1895. He received the
Nobel Prize in Physics for this 1901 (the very first Nobel prize). Rontgen was working on
investigating cathode rays in an evacuated tube and a fluorescent screen painted with Barium
accidently left near the tube. The screen was glowed green and even though the tube was
covered with a black screen. He investigated this effect further and showed that the radiation
could pass through matter - including human skin and named these mysterious rays.Latter, it
was called as X-rays.
We now know that X-rays are part of the Electromagnetic (EM) spectrum.
Visible radiation is also part of the EM spectrum but only occupy a tiny range. The EM
spectrum is shown in figure 1.

Figure 1: Electromagnetic Spectrum of radiation


(From B. D. Cullity and S. R. Stock, Elements of X-Ray
Diffraction, 3rd Edition, Prentice Hall).
Depending on the wavelength and hence energy the EM spectrum is dividedinto different
regions
The relation between the Energy (E) and wavelength () is given by

h
E
c

Where h is Planck's constant (6.62610-34Js-1) and c is the velocity of light(3108ms-


1
).Typically for X-rays, energy is given in units of eV or electron-Volt where1 eV = 1.6 10-
19
J.

Production of X-Ray
What is X-ray? How are X-rays produced?
X-rays are produced when the electrons are rapidly decelerated at target materials. There are
different sources of X-rays, used in characterisation of materials.
1. X-ray tube - most commonly used for table top X-ray machines.
2. Synchrotron radiation - this is approximately 105 more intense than X- ray tubes.

Mainly used for thin film measurement, surface properties, and X-ray spectroscopy from
small volumes. The schematic of the X-ray tube is shown in figure 2.

Figure.2: Schematic of X-Ray tube


(From B. D. Cullity and S. R. Stock, Elements of X-Ray
Diffraction, 3rd Edition, Prentice Hall).
The X-ray tube consists of a cathode and anode. The cathode acts as the source of electrons
which are accelerated and strike the anode (for safety issues the anode is grounded and the
cathode is maintained at a high negative potential with respect to the anode) which acts as the
source for producing X-rays. Most of the energy of the incoming electrons gets converted to
heat (X-ray production is a highly inefficient process. Typically 1% of the electrons get
converted to X-rays).So cooling water is owed through the anode for heat extraction. X-rays
are produced in all directions and come out of the tube through the Beryllium window while
the rest are blocked by the metal shielding.
The emission of X-rays depends on the energy of the electrons striking the anode target,
which in turn depends on the applied voltage. A plot of the X-ray intensity vs. wavelength is
shown for a Mo target in figure 2. Different plots are obtained depending on the applied
voltage. Below 25 kV the spectrum obtained is a continuous curve with a short wavelength
limit (SWL) rising to a gentle peak and then tapering off at the limit of large wavelength. At
25 kV the continuous background has 2 sharp peaks superimposed on it.
Continuous X-rays
These are obtained when the accelerated electrons interact with the atoms (Electrons) in the
target material. The incoming electrons transfer their energy to the X-rays that are then
emitted from the sample. The maximum energy (or the minimum wavelength) X-rays are
produced when all the energy is transferred. This is the short wavelength limit (SWL) of the
continuous X-rays. The wavelength is related to the applied voltage by the following relation.

Figure 3: X-ray spectrum from Mo as a function of applied voltage.


(From B. D. Cullity and S. R. Stock, Elements of X-Ray
Diffraction, 3rd Edition, Prentice Hall).
Thus, as the applied voltage increases the SWL decreases. For a typical applied voltage of 10
kV the SWL value is 1.24 . The continuous X-rays are also called Bremsstrahlung radiation,
which is German for braking radiation. Since the radiation are produced by deceleration of
the incoming electrons hitting the target anode. The intensity of the continuous X-rays (Icont)
is directly proportional to the area under the curve in figure 3. This intensity depends on the
following terms

Where A is proportionality constant, i is the beam current, Z is the atomic number, V is the
applied voltage, and m is an empirical constant (usually has the value 2).

Characteristic X-rays

As seen in figure 3 a certain voltage sharp lines are seen in the X- ray spectrum. These sharp
lines are typical of a given material and are the characteristic X-rays. These are superimposed
on the background of the continuous X-rays which are always present and depend on the
applied voltage. The characteristic lines are narrow and appear at specific wavelengths that
are independent of the applied voltage (above a certain threshold) as shown in figure 4. These
lines are denoted by K, L, M followed by a Greek symbol ,,.K lines have the shortest
wavelength (highest energy). L lines are longer than K. M is longer than L and so on. Within
the K lines K has a longer wavelength than K. For some elements the K can be further
resolved into K1 and K2.

Figure 4: Characteristics X-ray spectrum from Mo at 35Kv.


(From B. D. Cullity and S. R. Stock, Elements of X-Ray
Diffraction, 3rd Edition, Prentice Hall).

The intensity of any characteristic line, measured above the continuous spectrum, depends
both on the tube current i and the amount by which the applied voltage V exceeds the critical
excitation voltage for that line. For a K line, the intensity is given by

where Bis a proportionality constant, VK the K excitation voltage, and n a constant with a
value of about 1.5. The intensity of a characteristic line can be quite large: for a given an
example of typical values as shown in figure 4, for a Mo target K wavelength is 0.7 , L
wavelength is 5 M wavelength is 35 .Similarly, for a Cu target K wavelength is 1.54
while L wavelength is 13 .For Mo, we can also resolve the K lines.K1 wavelength is 0.709
, K2 wavelength is 0.714 , K1 wavelength is 0.632
Mechanism of X-rays production
How do we understand the formation of X-rays?

As shown in figure 5, in Bremsstralung or continuous radiation incoming electrons are


deflected by the electrons in the target material. The energy lost is converted to photons -
specifically X-rays. In characteristic X-rays the incoming electrons have enough energy to
create a hole in the core shell by knocking of the electron. When this hole is filled with
electrons from the outer shell the difference in energy is given out as X-rays. A simple way to
understand this is to use the 'planetary' model for the atoms where the electrons revolve
around the nucleus in specific shells. A hole is created in the K shell. When electrons from
the L shell fall into the K shell the X-rays that are generated are called K. Similarly, the K
shell hole can be filled by electrons from the M shell and these are called K. The energy of
the X-ray radiation is equal to the energy difference between the two energy levels.

It is straightforward to see that K X-rays have a higher energy (lower wavelength) than K
X-rays since the energy difference between K and M is more than K and L. When a hole is
created in the K shell (by incoming electrons from the cathode) electrons from the L shell can
fall into the K shell and the energy difference is emitted as characteristic X-rays.

Figure 5: Schematic of energy transitions in an atom.(From B. D. Cullity and S. R. Stock,


Elements of X-RayDiffraction, 3rd Edition, Prentice Hall).
The energies and the wavelength of the lines depend on the target material and hence they are
'characteristic' of the particular element. These lines are very narrow since the core levels are
very narrow (in energy) unlike the valence levels. Changing the applied voltage (above the
threshold voltage) does not change the peak position. The intensities of these lines are much
higher than the continuous X-rays, which serve as the background. Characteristic X-rays
were discovered by Mosley and this is what is used for X-ray diffraction.
Mosley Law
The characteristic x-ray lines were discovered by W. H. Bragg andsystematized by H. G.
Moseley. The latter found that the wavelength ofany particular line decreased as the atomic
number of the emitter increased.In particular, he found a linear relation (Moseley's law)
between the square root of the line frequency and the atomic number Z:

whereCand are constants. This relation is plotted in Fig 6 for the K1 and L1 lines, the
latter being the strongest line in the series. These curves show, incidentally, that lines are not
always of long wavelength : the L1 line of a heavy metal like tungsten, for example, has
about the same wavelength as the K1line of copper, namely about 1.5A.

Figure 6: Moseleys relation between \/v and for two characteristic lines. .(From B. D. Cullity
and S. R. Stock, Elements of X-RayDiffraction, 3rd Edition, Prentice Hall).
X-ray absorption
X-ray production in the X-ray tube as shown in above figure 2. Since X-rays are EM waves
the treatment is similar to how visible radiation interacts with a solid. If we have a beam of
intensity I falling on sample the decrease in intensity is directly proportional to the distance
travelled. Schematically, this is shown in figure 7 and expressed mathematically for a one
dimensional case as

Figure 8: Schematic of linear absorption of X-rays through a solid

Where is called the linear absorption coefficient. The negative sign arises because the
intensity reduces with distance within the material. Solving this equation 4, using the
boundary condition that when x = 0, I = I0, gives

The absorption coefficient here has units of mwhich is why it is called linear absorption
coefficient. There is another number that is normally used called mass absorption coefficient.
This is defined as ratio of linear absorption coefficient to the mass absorption
coefficient(/),where is the density of the material. The unit for the mass absorption
coefficient is m2/kg.
The mass absorption coefficient is constant for a material and does not depend on the
physical state. But it does depend on the wavelength of the radiation used.
X-ray filters
In X-ray diffraction we need a monochromatic (single wavelength) X-ray source but the
output of an X-ray tube typically consists of a continuous background with some
characteristic sharp peaks. Ideally, we need to filter the background and eliminate some of the
sharp peaks and this we can do using the concept of x-ray absorption. The idea is shown
schematically in figure 9 for the case of Cu radiation.
The unfiltered Cu radiation shows two distinct peaks K and K. While K has a higher
intensity than K the presence of the second peak will affect diffraction studies by producing
satellite peaks. In order to minimize the intensity of the K line the unfiltered radiation from
Cu (Z=29) is passed through a Ni filter (Z=28). Figure 9 shows that the K-edge absorption
peak for Ni lies between the Kand K lines of Cu.

Figure 9: Output from a Cu source without a filter and after passing throughthe filter.(From
B. D. Cullity and S. R. Stock, Elements of X-RayDiffraction, 3rd Edition, Prentice Hall).

Thus, the Ni selectively absorbs the K line of Cu and hence the final output has a higher
intensity ratio between the two characteristic lines of Cu. Thicker the filter higher is the
intensity ratio of K/K but the overall intensity also goes down. Typical filter thicknesses
are chosen so that the ratio of the intensity of the K and Kline is 500:1. The choice of filler
material depends on the X-ray source. The filters materials usually have atomic less than and
close to the atomic number of the source. Some typical X-ray sources and their filters are
shown in table 1.
Table 1: X ray sources with atomic number given in brackets and filter.

X-ray diffraction
In X-ray diffraction we focus on a combination on both, how X-rays interact with crystalline
solids, specifically the phenomenon of diffraction. Diffraction by light waves is a well known
phenomenon. X-rays have wavelength of the order of 01 - 10 . Crystals have lattice
constants and hence interplanar spacing around 2 - 6 . Thus a crystalline material naturally
serves as a ruled grating with the ability to scatter X-rays producing maxima and minima i.e.
diffraction. Diffraction using X-rays was first shown by German physicist von Laue in 1912
where he used a copper sulphate crystal (CuSO4 with a triclinic structure) to get diffraction
patterns from X-rays. This work was carried forward by a father-son scientist team W.H.
Bragg and W.L. Bragg who managed to express the condition for diffraction in a
mathematical form. This was called Bragg's law. They were also able to solve the structure of
sodium chloride using X-rays thus proving the power of X-ray diffraction to solve crystal
structures.

Bragg's law
Two geometrical facts are worth remembering:
(1) The incident beam, the normal to the reflecting plane, and the diffractedbeam are always
coplanar
(2) The angle between the diffracted beam and the transmitted is always 2. This is known as
the diffraction angle, and it is this angle,rather than, which is usually measured
experimentally.
From figure 10 x-rays are incident at an angle on two planes with spacing d. X-rays
reflected from the bottom plane have to travel an extra distance, whichis given by 2dsin
(from geometry). This is the then the path differencebetween the x-rays reflected from the
material. For constructive interferencethis path length has to be an integral multiple (n)of the
wavelength. Thus,Bragg's law can be stated as

Here, n is an integer and can take values 1, 2, 3 and so on. This represents the order of
reflection. Bragg's law is the most important law in diffraction.

Figure 10: x-rays are incident at an angle on two planes with spacing d.
Let us use an example to understand Bragg's law. Consider a metal with fcc crystal structure,
Nickel (Ni) with lattice constant a of 3.52 . Cu K radiation of wavelength 1.54 is
incident on Ni. Considering only first order reflection (n=1) equation 4 can be written as

Thefirst criteria is that sin cannot be greater than 1 so that 2d ord /2 Thus, using
Bragg's law only those d-spacing greater than halfthe wavelength of X-rays used will produce
diffraction. This sets a lowerlimit on the measurable d-spacing and dictates the choice of X-
rays used fordiffraction. On the other hand, if we use too low a wavelength the angles ()will
be very small and hence it will be hard to differentiate one line from the other. Typically, for
metals Cu K is used as the X-ray source. If we consider the 100 family of planes for Cu, the
d-spacing is the same as aand using equation 4, = 12:64. For 110,d = a/2 = 2:49 and=
18:21. For 111, d = a/3 = 2:03 and = 22:27. Thus as d-spacing reduces the diffraction
angle increases.

Apart from Cu K another commonly used X-ray source is Mo K witha wavelength of 0.71
. Since the wavelength is smaller the angles will also be smaller, for the same d-spacing.
Thus, if we use Mo for the above Niexample the 111 line will fall at = 10:07 instead of
22:27. Mo sources are normally used for small molecules where the d-spacing is smaller and
we need a smaller wavelength to obtain diffraction, see equation 5.

X-ray spectrometer
Experimentally Bragg's law can be used in 2 ways:
1. Use X-rays of single (monochromatic) and known wavelength () and measure the
diffraction angle () and use that to calculate the d-spacing and hence the crystal structure.
This is called structure analysis.
2. Alternate is to use planes of known spacing (d), measure and from this calculate . This
technique is called X-ray spectrometry and is a way of doing chemical analysis with X-rays.
We can also use this to get a true line source for structure analysis.

Figure 10: Schematic of X-ray spectrometer. Taken from Elements of X-raydiffraction - B.D.
Cullity.
From figure 10, the source is an X-ray tube which emits a continuous spectrum of X-rays
with some characteristic sharp peaks (depending on the tube voltage being above the
threshold).The X-rays fall on a crystal with known d-spacing. Thus, different X-rays are
diffracted at different angles which are measured by the detector that is rotated. Thus, we can
get a plot of I vs. or I vs 2. Energy of the X-ray source. This can be used for calibrating
new X-ray sources and chemical analysis. If instead of the detector we had a narrow exit slit
that only the wavelength corresponding to the slit angle will be emitted while the others will
be stopped. Thus using the X-ray spectrometer a very narrow monochromatic source can be
obtained especially for use in high precision X-ray diffractometers.

Diffraction methods
From the Braggs law there are two parameters that we can vary and . Based on
these parameters there are essentially three diffraction methods as tabulated in table
2

Table 2: X-ray diffraction methods

Laue method
Laue method was the first diffraction method used. A single crystal (fixed orientation) is
required for this method. The technique use white radiation (range of wavelengths), typically
unfiltered radiation from a X-ray tube. This falls on a single crystal that is fixed. Thus, the
diffraction angle, is fixed for every diffraction plane and for that particular value a certain
wavelength will get diffracted, using Braggs equation. Thus, each diffracted beam will
correspond to a certain wavelength which then falls on the film. Based on how the film is
positioned there are two types in Laue method as shown in figure 11.
1. Transmission Laue method - The film is placed in the forward diffraction (behind the
crystal) so that forward scattered radiation is deflected. The film is at and perpendicular to the
incident beam and the diffracted beams are partially transmitted through the sample before
striking the film.
Figure 11: (a) Transmission Laue method. (b) Back reflection Laue method. (From B. D.
Cullity and S. R. Stock, Elements of X-Ray Diffraction, 3rd Edition, Prentice Hall).

2. Back reflection Laue method - The film is placed between the incident beam and the
crystal so that the back reflected rays are used to form the image. The incident beam passes
through a hole in the film and falls on the crystal.

Both techniques produce an array of spots on the film. This array of spots is called a
diffraction pattern.

Rotating crystal method


As shown in figure 12, this is another technique that is used for single crystals. This
technique uses a monochromatic X-ray source (x-rays from a tube passed through the
appropriate filter). The film is placed around the crystal in a cylindrical fashion. The crystal is
rotated about its axes and as it rotates different sets of planes will form the correct Bragg
angle for diffraction and produce spots. The reflected beams are located on the cones with the
zone axis as the axis of the cone. This coincides with the axis of rotation. The diffracted spots
on the films, when it is unrolled will then lie of horizontal lines. The each lineis
corresponding to diffraction from a set of planes corresponding to a particular zone axis.
Usually the crystal is rotated about one particular axis so that not all planes will satisfy the
diffraction condition. The rotating crystal method can be used to find the unknown crystal
structure of the material but the drawback is that a good quality single crystal is needed for
this.
Figure 12: Rotating crystal method of diffraction.(From B. D. Cullity and S. R. Stock,
Elements of X-Ray Diffraction, 3rd Edition, Prentice Hall).
Powder method
This is similar to the rotating crystal method, in that monochromatic x-rays are used to
generate the diffraction pattern. Here, the angle is varied not by rotating the sample but by
having small crystallites with all possible orientations (all possible). Usually a powder
sample is used, where the individual 'grains' can be considered as individual crystals (not
always). Thus, some grains will have 100 orientations; some will have 111 orientations and
so on. Each of these will diffract at certain Bragg angle so that we can consider the diffracted
rays as forming a cone, with the crystal as the apex, as shown in figure 13.
The film is usually wrapped around the sample, in the form of a cylinder. When the cones
intersect with the film they leave traces(lines which are actually arcs of circles) with the
central spot corresponding to the zero or 180 position. This is shown schematically in figure
13 with the film also laid out flat. This type of arrangement is called Debye-Scherrer
method.
The distance of the lines from the central spot corresponds to the diffraction angle (2) since
this represents the angle between the incident beam and the diffracted beam. From measuring
the angles and knowing the wavelength of X-rays, we can use Bragg's law to find the d-
spacing and from that the lattice constant and the crystal structure.
The diameter of the camera also decides the spacing between the diffraction lines. If the
camera diameter is small then the spacing is small and it will be hard to distinguish between
nearby lines. If the diameter is large then the intensity of the diffracted beams reaching the
film is lower. One of the disadvantages of using the film to record patterns is that the
quantitative information on the intensity of the lines is lost.

Figure 13: Diffraction cones from a powder sample intersecting the film.(From B. D.
Cullity and S. R. Stock, Elements of X-Ray Diffraction, 3rd Edition, Prentice Hall).

Modern X-ray diffraction systems

Modern X-ray diffraction systems replace the film with an x-ray spectrometer which gives
the intensity of the scattered x-ray at a particular angle as shown figure 14. The x-ray tube is
on the left and is the source. The sample is placed in the middle and the diffracted rays fall on
the detector on the right. As the source rotates by angle 2 the detector rotated by angle 2
and at each angle the intensity is recorded. Finally, Intensity vs. 2 plot is obtained where
there are peaks corresponding to diffraction from the various planes in the polycrystalline
material. A typical XRD plot for Si is shown in figure 15
Figure 14:A Rigaku X-ray diffractometer.

Figure 15: A typical powder pattern from Si.


Intensity of diffracted beams
The intensities of the lines are all different as shown in XRD pattern of Si. We understand the
position of the lines is given By Bragg's law and knowing the lattice constant and the crystal
structure. It is possible to calculate the 2 values but what decides the intensity and the
presence/absence of some lines? This is dictated by the position of the atoms in the lattice.
Thus the crystal structure plays a role and also the number and type of each atom. If we have
a compound or intermetallic the intensities will depend on the position and amount of each of
the constituentatoms. Similarly, in the case of intermetallics order-disorder
transformationscan also affect the XRD patterns.
For example, consider figure 16 and 17 which shows the base centered and body centered
orthorhombic structures and their diffraction. For the base centered structure, in the c axis,
the interplanar spacing is c and the plane is 001. For the body centered structure the
interplanar spacing is c/2 and the plane is 002. Thus, 001 diffraction will be present in the
base centered structure but for the body centered structure it will be out of phase with the 002
planes and will be absent

Figure 16: Body centered and base centered orthorhombic structure.(From B. D. Cullity and
S. R. Stock, Elements of X-Ray Diffraction, 3rd Edition, Prentice Hall).

Figure 17: Diffraction from 001 and 002 orthorhombic planes. For the body centered the 001
lines are absent. (From B. D. Cullity and S. R. Stock, Elements of X-Ray Diffraction, 3rd
Edition, Prentice Hall).
Thus, the presence of the extra atom in the unit cell at the center can cause a difference in the
XRD pattern of a material. This same argument is true for a simple cubic and body centered
cubic lattice. Thus 100 reflections is possible in the simple cubic lattice but not in the body
centered cubic lattice. To understand how intensities vary for the different peaks we need to
look at the interaction of x-rays with the crystal. This can be understood by considering the
interaction of x-ray with an electron, then an atom (group of electrons since X-rays do not
interact with the nucleus), and finally a crystal (group of atoms with added periodicity).

Scattering by an electron
X-ray is electromagnetic radiation i.e. they have mutually perpendicular electric and
magnetic fields. Electrons are negatively charged particles that are affected by these electric
and magnetic fields. When X-rays interact with electrons it causes it to oscillate. The
oscillating electron will in turn emit X-rays - this is called scattering. There are two kinds of
scattering.

1. Coherent scattering - emitted X-rays have the same wavelength (same energy) as the
incident X-rays. This is also called elastic scattering and the scattered radiation has a definite
phase relation with the incident X-rays.
2. Incoherent scattering - the X-rays lose some energy during scattering so that the final
energy is lower (wavelength is higher) than the incident energy. There is no definite phase
relation to the incident radiation. This is also called inelastic scattering.

In the case of X-ray diffraction we are interested in the elastic scattering component. Any
inelastic scattering will only add to the background. Another component to the background is
x-ray fluorescence so the choice of the x-ray source depends on the type of material (Cu is
not normally used for Fe due to strong x-ray fluorescence). For elastic scattering the scattered
radiation is phase shifted from the incident beam by /2 or has a path difference of /2.
The scattering takes place in all directions but the intensity depends on the angle of
scattering. The expression for this is given by J.J. Thompson.
Where, Ir is the intensity at a distance r from the electron and is the angle between the
recoiling electron and the scattered x-ray. In the case of diffraction we want the intensity in
terms of the angle between the incidents and scattered radiation (2). This is given by
(schematically shown in figure 18)

This is the Thompson equation for the scattering of x-rays by a single electron. The intensity
decreases as square of the distance from the electron. Scattering is high in the forward or
backward direction (2 = 0 or 180).
The term (1 + cos22/2) is called the polarization factor.

Figure 18: Coherent scattering of x-rays from a single electron.(From B. D. Cullity and S. R.
Stock, Elements of X-Ray Diffraction, 3rd Edition, Prentice Hall).

The x-ray can also undergo inelastic interaction with the electron. This is called the Compton
effect and is shown schematically in figure 19. Compton scattering is usually observed for x-
ray interaction with loosely bound electrons in an atom i.e. the valence electrons. The X-rays
lose energy to the electron so that the final wavelength is higher than the initial wavelength.
The change in wavelength is given by the scattering angle by
Figure 19: Compton Effect - scattering of x-rays from a single electron with loss of
energy..(From B. D. Cullity and S. R. Stock, Elements of X-Ray Diffraction, 3rd Edition,
Prentice Hall).

Scattering by an atom
An atom consists of electrons (loosely and tightly bound) and a nucleus. Nucleus is
not involved in x-ray scattering since its extreme mass means that x-ray don't have
sufficient energy to oscillate it and produce other x-rays.So scattering by an atom
refers to scattering by the electrons in the atom.For scattering of x-rays by an atom,
a scattering factor f is defined which is called atomic scattering factor. This is given
by

For 2 = 0 f = Z, where Z is the atomic number while it is lower for other angles. The
scattering factor also depends on the wavelength of the X-rays. For shorter wavelength, f is
lower since the path difference will be higher with respect to the wavelength. Typically, f is
plotted as a function of angle and wavelength, as shown in figure 20 for Cu.

Figure 20: Atomic scattering factor for Cu.(From B. D. Cullity and S. R. Stock, Elements of
X-Ray Diffraction, 3rd Edition, Prentice Hall).
Scattering by an unit cell
We can consider the unit cell as a group of atoms arranged in a periodic fashion. Given that
the atoms are arranged in a crystal with three dimensional periodicity x-ray scattering only
takes place at certain directions, diffraction, which obeys Bragg's law. If Bragg's law is not
satisfied then there is no diffraction and hence no x-ray scattering. Thus, we only need to look
at the x-ray intensity in directions where Bragg's law is satisfied and the intensity depends on
the types and positions of the atoms in the lattice. Also, we only have to consider only one
unit cell since the crystal is periodic.
Consider the one set of planes shown in figure 21. For simplicity let these planes be of the
form (h00) planes so that the d-spacing is equal to a/h. This is from the definition of Miller
indices where (hkl) gives the intercepts of the planes with the axes. X-rays are incident on
this plane at the Bragg angle so that diffraction condition is satisfied. Consider another set of
atoms located at position B, which is at a distance x from A. The path difference between the
x-rays reflected from A and B is then given by (AB/AC) or (x/ (a/h).This can be converted
to phase difference by multiplying with 2. Thusthe phase difference is given by 2h x/a,
which can be written as 2huwhereu represents the fractional coordinate for the atom at
position B. We canextend this argument to 3D for any general plane (hkl) with atoms
locatedat fractional coordinates (uvw). The total phase difference is then given by

This represents the phase difference between x-rays reflected from the unit cell at different
positions. Combining this with the atomic scattering factor of the atoms located at the
different positions we can define a new term called the structure factor, F. The structure
factor with an atom located at position (uvw) in an unit cell is given by

If there are N atoms in the unit cell and the nth atom has structure factor fn and is located at
(unvnwn) then the structure factor for the unit cell, for some plane (hkl) is given by
The atomic structure factor thus defined as

Calculation of Structure Factor with single atom basis


Using equation 7 it is possible to calculate the structure factor for a (hkl) plane of an unit cell
once the atom scattering factors and positions are known. The structure factor is related to the
intensity of the x-ray diffracted from that plane. Thus if the structure factor for a given plane
is zero then there will be no diffracted intensity, even though Bragg's law is satisfied. Thus,
Bragg's law only decides the 2 value for a given plane while structure factor decides the
intensity.

Simple cubic
In a simple cubic unit cell there is only one atom per unit cell, located at(000). So N = 1 and
(uvw) is (000). So using equation 7 the structure factor for a (hkl) plane simply becomes Fhkl=
f. Thus, for a simple cubic structure diffraction is possible for all possible planes since the
structure factor is a constant, equal to the atomic scattering factor. Thus, all planes can be
seen in the diffraction pattern of a simple cubic structure. The intensities are still not the same
since there are other factors involved.
Body centred cubic
In a body centered cubic structure there are 2 atoms per unit cell, at (000) and (1/21/21/2).
These represent the fractional coordinates of the atoms in the unit cell. Substituting them in
equation 7 we can get the expression for the structure factor as

From equation 9 it can be seen that when h+k+l is even (expi(h + k + l)) is equal to 1 and
when h + k + l is odd it is -1. So the structure factor is

Thus, diffraction intensities are only found for specific hkl planes in bcc whichsatisfy the
condition in equation 10 i.e. h+k+l should be even.
Face centred cubic
In the face centred cubic structure there are 4 atoms per unit cell, one at the corner and 3 on
the face centres. Once again using equation 7 the expression for the structure factor simplifies
to

The rules for diffraction intensities for fcc is then

Thus, for fcc structure diffraction lines are seen for planes like (111), (200),(220), (311),
(222) where the indices are all even or odd. Other diffraction lines are absent.

Hexagonal close packed


In the case of the hcp structure, the fractional coordinates for the atoms are (000) and ( 1/3
2/31/2). The equation for the structure factor then becomes

It is important to understand that the structure factor calculations do not depend on the size
and shape of the unit cell. The structure factor only depends on the position and type of atoms
in the unit cell. The calculations derived above are for unit cells with only one type of atom.
If we have more than one type of atom then the atomic scattering factors are also different
and the structure factor rules are no longer valid.

Structure factor with multi-atom basis


For unit cells with more than one type of atom - compounds or intermetallics the structure
factor can be still calculated using equation 7 except that the atomic scattering factor for each
type of atom needs to be taken into account.

For example, consider the case of CsCl. This has a bcc structure with the Cl-ions at the corner
and the Cs+ion at the centre of the unit cell. Then the structure factor for this unit cell, using
equation 7 is given by
Using the same conditions for bcc the structure factor values are

Thus, unlike a bcc unit cell with one atom basis, the intensity of the diffraction line does not
go to zero when h+k +l is odd but has a finite value (the intensity will be low since it is
proportional to the difference of the atomic scattering factors).

X-ray intensity
In the absence of all other factors the intensity of the diffracted x-ray is equal to the square of
the structure factor. But there are a number of other factors that affect the intensity as follows.

Multiplicity factor
The multiplicity factor refers to the relative proportion of the planes contributing to
diffraction. Different planes have different multiplicity values, which are usually tabulated.
The multiplicity factor depends on the crystal structure since the planes must have the same
d-spacing.

Figure 22.Multicity Factors for powder pattern.(From B. D. Cullity and S. R. Stock, Elements
of X-Ray Diffraction, 3rd Edition, Prentice Hall).
Lorentz-polarization factor
The Lorentz factor is a trigonometric factor that relates to the distribution of planes as a
function of 2. For a powder sample, with randomly oriented particles, the integrated
intensity is area under the curve of a reflection at a given Bragg angle which depends on the
no. of particles with that orientation. Even the particles are oriented at random this number is
not a constant but depends on the value of the Bragg angle. This dependence is called the
Lorentz factor and is given by

Usually, the Lorentz factor is combined with the polarization factor (seen in the Thompson
equation) to form the Lorentz-polarization factor.

The Lorentz-polarization factor as a function of Bragg angle is shown in figure 23.

Figure 23: Lorentz-polarization factor as a function of Bragg angle.(From B. D. Cullity and


S. R. Stock, Elements of X-Ray Diffraction, 3rd Edition, Prentice Hall).
Absorption factor
The x-ray intensity also depends on the absorption of the specimen being investigated. This
also depends on the geometry of the setup. In the case of the diffractometer the absorption
factor is independent of the Bragg angleand does not affect the relative intensities of the
different lines.
Temperature factor
Atoms in the lattice are constantly vibrating about their equilibrium position. As the
temperature increases, this vibration amplitude increases. One effect of this vibration is that
the lattice spacing constantly changes so that the overall intensity of a line decreases with
increasing temperature. At the same time background scattering increases. For a given
temperature the effect is pronounced at higher Bragg angles since the d- spacing is smaller.
The temperature effect is usually determined experimentally and written in the form exp(-
2M).
Putting the various factors together the intensity of the x-ray diffraction line is given by

Here, I refer to the relative integrated intensity (area under the curve of the diffraction line),
here F is the structure factor for the (hkl) plane and p is the multiplicity factor. The other
factors are the Lorentz-polarization factor and the temperature factor. The absorption factor is
not included for the relative intensities since it does not depend on Bragg angle. The intensity
given here assumes a random polycrystalline sample - powder or film.

Application of X-rays

Powder diffraction patterns


The original reason for doing x-ray diffraction is to identify the structure of the unknown
material (metals, ceramics and polymers). For such materials powder patterns from
polycrystals are used for identifying the crystal structure. Powder patterns gives two useful
information
1. The shape and size of the unit cell - this is from the position of the diffraction lines (2
2. The arrangement of atoms in the unit cell - this is from the relative intensities of the
different lines.

Indexing pattern for cubic crystals


A cubic crystal gives diffraction lines where the angle (2) obeys the following
relation

Where, a is the lattice constant, is the x-ray wavelength, and (hkl) refers to Miller
indices of the plane. Equation 1 is obtained using Bragg's law and the fraction is a
constant for diffraction lines from a given x-ray source. Since, hklare integers sis
also an integer and can only take certain values. The values that s can take changes
for the different cubic systems (sc, bcc, and fcc) and this is based on the structure
factor rules. The problem is finding the values of s for the different 2values. The s
values for the different cubic systems are

Table 3:2 values for Al with corresponding values of sin2/s for the various cubic systems.

From table 3, Al crystallizes in afcc structure. The lattice spacing can be calculated using
equation 1 where the value of the constant from table 3 is 0.036.

From equation 2 the lattice constant a of Al is 4.06 . Given that the density of Al () is 2.7
gcm-3 it is possible to calculate the number of atoms per unit cell, Z. This is given by the
relation

Where, NA is Avogadro's number. From equation 3 the value of Z is 4. Thus, Al has afcc
structure with 4 atoms per unit cell.
Crystal Size effect
Typical grain sizes in metallurgical samples can be from 0.1 - 1000 nm. The higher end is
usually when we have large secondary grain growth in thin films. Nanocrystalline samples
typically have grain sizes from 0.01 - 1 nm. The most accurate way to measure grain size is
by microscopy techniques X-rays are especially useful for grain sizes below 1 nm. In a
diffractometer setup (where line intensity is measured) smaller grain sizes leads to peak
broadening.

Figure 24: Effect of fine particle size on diffraction curves.(From B. D. Cullity and S. R.
Stock, Elements of X-Ray Diffraction, 3rd Edition, Prentice Hall).

Broadening occurs because as the grain size decreases the number of planes in a crystal that
diffract at the same angle decreases. This means that for small deviations from the Bragg
angle the scattered intensities do not cancel out completely due to destructive interference.
This leads to a broadening of the peaks. The width of the diffraction curve of Fig. 24 a)
increases as the thickness of the crystal decreases. The width B is usually measured, in
radians, at an intensity equal to half the maximum intensity.The approximate measurement of
B we can take half the difference between the two extreme angles at which the intensity is
zero, or

The peak width, B, is related to the grain size (or particle size in a powder sample) t and
Bragg angle, Bby
The effect of peak broadening is greater for larger Bragg angle peaks sincecosB is in the
denominator. Consider the case of a crystal with a Bragg angle of B = 45. Also, let the
incident x-ray radiation be the Cu Kradiation with wavelength of 1.54 . Then, using
equation 1 we can calculate the peak broadening for different grain size. If t = 10m then the
broadening is 0:001 (too small to be detected). When t = 0:1m then the broadening
becomes 0:11. As the size reduce further to 0:01m the broadening becomes 1:1which is
appreciable. A grain size of 0:01m or 10 nm corresponds to just 25 planes (if we take d
spacing to be 4, reasonable value) so that destructive interference does not occur for
sufficiently wide deviations from the Bragg angle. The peak broadening effect due to
decreasing grain size can be seen for Ni in figure 2. Thus, x-rays can be used to estimate
grain sizes especially for nanocrystalline grains, at least in a semi qualitative way. For grain
size estimation we should eliminate other sources of broadening. These can be of two types
1. Instrumentation - this can be eliminated by using a standard material with grain size
> 1 m and measuring its peak width.
2. Sample - need to eliminate other sources of broadening like non uniform strain.
Usually, grain size measurements are best performed on loosepowder compacts using high
Bragg angle peaks.

Residual stress measurement


Another source of broadening of x-ray peak is cold working leading to non- uniform strain in
the material. This is because plastic deformation causes change in the d-spacing of the planes
and this can change the Bragg angle. If there is uniform strain in the material then all the
grains are equally affected. Hence there is no broadening but the peak position shifts. If there
is non-uniform strain some grains are under tension and some are under compression. In this
case the peak position does not shift but broadening increases. This is summarised in figure
25. If B is the broadening then it's relation to strain can be derived by

Where d/d represents the non-uniform strain in the material. Cold working a material can
have the following effects
1. Reduction in grain size
2. Change in shape of the grain size
3. Stacking faults
All three have the effect of distorting the lattice and broadening the x-ray peaks but it is hard
to distinguish the dominant factor.
Figure 25: Diffractometer traces of cold-rolled and annealed brass samples and Effect of (b)
uniform strain and (c) non-uniform strain on peakposition and peak width in XRD. (From B.
D. Cullity and S. R. Stock, Elements of X-Ray Diffraction, 3rd Edition, Prentice Hall).

Phase diagram determination


The following are the principles for collecting x-ray diffraction patterns for phase diagram
determination
1. Each alloy must be at equilibrium at the temperature of interest. For high temperature
phases not stable at room temperature there are two options for studying the crystal structure.
(a) Quench to room temperature and do diffraction.
(b) Use x-ray diffraction with high temperature attachment for direct determination. This
option is preferred when available for it eliminates the need for preparing large number of
samples.
2. The phase sequence: a horizontal line (constant temperature) must pass through a single
phase region and 2 phase region alternatively. A line cannot pass from one 2 phase region to
the next without passing through a single phase region, can be a line compound. As shown in
figure 26 and 27
Figure26:Phase diagram and lattice constant of a hypothetical binary phase
diagram.(From B. D. Cullity and S. R. Stock, Elements of X-Ray Diffraction, 3rd Edition,
Prentice Hall).

Figure 27: XRD patterns for different alloys from the hypothetical binary phase diagram.
(From B. D. Cullity and S. R. Stock, Elements of X-Ray Diffraction, 3rd Edition, Prentice
Hall).
Super lattice structures
These are also called order-disorder transformations. Ordered structures are also called super
lattice structures. The new lines seen in the diffraction pattern are called super lattice lines.
The original lines are called fundamental lines.
In a random solid solution, atoms are arranged (more or less) at random on a
crystalline lattice is known as disorder phase
At a critical (low) temperature, the atoms may spontaneously order (A-atoms
preferentially surrounded by B-atoms, and vice versa) as shown in figure 28.

Figure 28: Ordered and disordered configuration in AuCu3.(From B. D. Cullity and S. R.


Stock, Elements of X-Ray Diffraction, 3rd Edition, Prentice Hall).

To understand the formation of super lattice lines in XRD consider the example of AuCu3.
The disordered and ordered structure for this is shown in figure 6. AuCu3 has an fcc structure
with 4 atoms per unit cell. From the formula, there are 3 Cu atoms for 1 Au atom. In the
disordered structure, the 4 atoms are randomly located in the unit cell while in the ordered
structure, Au atoms are located at the corners and the Cu atoms are located at the face center
positions. The order-disorder transition temperature for this system is 390C.
Consider the completely disordered structure. The probability of a site being occupied by Au
atom is 1/4 while the probability of occupation by Cu is 3/4 .Hence it is possible to define an
average atomic factor term, fav that is given by

Where, fAuandfCu are the atomic scattering factors for Au and Cu. The disordered structure
can be considered as a regular fcc structure so that the structure factor Fhkl is given by
Using equation 11 we can see that the structure factor does not vanish for certain (hkl).

Thus, the ordered structure has extra diffraction lines, which are called super lattice lines.
This can be seen in the case of powder patterns of CuAu3 in figure 29 where extra lines are
visible.

Figure 29: Powder patterns of (a) disordered (b) partially ordered and (c) completely ordered
AuCu3.(From B. D. Cullity and S. R. Stock, Elements of X-Ray Diffraction, 3rd Edition,
Prentice Hall).

Texture
Texture refers to preferred orientation of grains of microstructure as opposed to random
orientation of grains. Texture can affect the properties since these are usually anisotropic.
Sheet texture is the most common form of texture and is represented by a plane (hkl) parallel
to the surface and a direction [uvw] in that plane representing the preferred orientation.
Preferred orientation is best represented by a graphical representation called pole figure,
shown in figure 30. Cold working or rolling can cause preferred orientation in a material with
most of the grains oriented with a certain plane parallel to the surface and a certain direction,
in that plane, roughly parallel to the direction of rolling. The advantage of using pole figures
is that it provides a visual representation of the angle between two planes.
.
Figure 30: Pole figure for (a) random (b) preferred orientation. R.D refers tothe rolling
direction and T.D refers to the transverse direction.(From B. D. Cullity and S. R. Stock,
Elements of X-Ray Diffraction, 3rd Edition, Prentice Hall).

Scanning Electron Microscopy (SEM)


Major components are the electron column consisting of an electron gun and the
electron lenses, and the control console consisting of a cathode ray tube viewing
screen and the scanning and control electronics for the electron beam.
The three dimensional appearance of the image is due to the large depth of field.
A scanning electron microscope (SEM) employs a probe lens to focus the electron
beam into a fine probe and scanning coils are used to scan the probe over the sample.
Resolution of the SEM is controlled by the probe lens. It is the inelastically scattered
electrons that provide information. Usually < 30 keV electrons are used in SEM.
In optical microscopy and TEM, information is collected continuously over the full
field of view (from all image points simultaneously) and focused by suitable lenses to
form a magnified image. In SEM, information is collected sequentially.
Electron microscopy instrumentation

Figure 31: Schematic of SEM with different components.

Electron sources
The first part of any SEM is the production of the electron beam. There are two main types of
sources, which differ in the physics of electron beam production.
1. Thermionic sources
2. Field emission sources

1. Thermionic sources

A thermionic source is a heated source. If sufficient energy is provided to anelectron in a


solid to overcome the barrier that prevents the electron from escaping (work function, ) then
the electron can be emitted. In thermionic emission, this energy is provided by heating the
source. The relation between the current density (J), the source temperature (T), and the work
function () is given by Richardson's law.
Where, A is the Richardson's constant (units Am-2K-2) and is constant for a given source
material. To increase the current density either temperature should be increased or a material
with a lower work function should be chosen. Usually, refractory materials like Tungsten are
used as thermionic sources. W has a high melting point of 3600 K and a work function of 4.5
eV. Lanthanum hexaborate (LaB6) is another good thermionic source material with a melting
point of 2500 K but with a lower work function of 2.4eV. The disadvantage of LaB6 is that is
a ceramic material and hence susceptible to thermal shocks. The source has to heat slowly to
the operating temperature and similarly cooled slowly during turn off.

Figure 32: Schematic diagram of a thermionic electron gun. (Transmission


Electron microscopy - Williams and Carter.)
2. Field emission sources
In field emission an applied voltage is used to generate a large electric field at a sharp tip.
This large electric field is used to the extract the electrons from the source to generate the
beam. The electron beam is generated due to tunneling from within the solid to vacuum. The
sharp tip is used to generate the large electric field since field (E) is equal to V/r.
The schematic of how field emission works in shown in figure 2.
Consider a metal with a work function. An electron removed from the metal, at a distance x
from the surface, is attracted to the now positively charged metal with a potential called
image potential. The image potential is given by

Table 1: Comparison of various electron sources. (TransmissionElectron microscopy -


Williams and Carter.)

Electromagnetic lenses
Since electrons have a charge, their direction of travel can be altered by an
electromagnetic field. An electron traveling in off-axis to a uniform magnetic field
follows a helical path. Electrons can be brought to focus by engineering the
electrostatic and/or magnetic fields. In the region of electron gun, the beam is
influenced by the electrostatic field. All the subsequent focusing is achieved by
electromagnetic lenses.
The condenser lens concentrates (or demagnifies) the beam of electrons into a small
area called a spot. It is like the condenser on an optical transmission microscope
which concentrates light from the light source (e.g,. a light bulb) into a small area as it
passes through the specimen slide. The size of the spot can be adjusted. It can be a
large area or it can be adjusted to be a small area. Condenser or spot size control is
one of the most important controls on an SEM.
In the electromagnetic lens, the intensity of the field (the magnetic flux) causes a
radial vector along the optical axis, so when an electron is accelerated through the
pole pieces, it takes a helical path through the lens. The rotational force is the product
of the electron velocity and the density of the magnetic flux. This vector interaction
also results in focusing as the strength of the lens is changed.
Focal length of the electromagnetic lens is controlled by varying the lens current. The
focal length is approximately proportional to V/(NI)2 where V is the accelerating
voltage, N is the number of turns in the magnet coil and I is the current.
Electron lenses demagnify the image of the beam crossover (with d0
heated electron gun) in the electron gun to the final spot size on the specimen of
~10 nm. This represents a demagnification by 5000 times.

These lenses are created with high precision and even a hairline scratch can distort
their magnetic field and will have to be replaced. Most electromagnetic lenses are
cooled with water to prevent extra heating.
Their functions are similar to optical lenses. A condenser lens can condense electrons;
an objective lens can focus electrons on the specimen, and a projector lens can project
an image onto a screen.
Figure 33: Schematic diagram of aelectromagnetic lens. (Transmission
Electron microscopy - Williams and Carter.)

Electron Beam Specimen Interaction.

When a focused nanometer sized electron beam enters a specimen, it interacts with a larger
volume in micrometer dimensions.

5 kV 10 kV 20 kV

Figure 33: schematic of electron beam interaction with specimen at different electron volts.
The electron beam undergoes both elastic and inelastic scatterings on the sample. The
electron beam interacts as negatively charged particles with the electric fields of the specimen
atoms

When the high energy electron encounters an atom, it first penetrates the outer, loosely
bound electron cloud, then it passes the inner, more tightly bound core shell electrons and
finally it may encounter the nucleus. The deeper the electron penetrates into the atom, the
higher the energy loss.

Secondary electron
(inelastic scattering)
Backscattered
electron
(elastic scattering) Primary electron

Outer shell electron


replaces
inner shell electron and
releases x-rays

Auger electron

Secondary electron
(inelastic scattering)

Figure 34: schematic of electron beam interaction with specimen atoms.

Backscattered and secondary electrons are the principal signals used to form images in
scanning electron microscopy.
SECONDARY ELECTRONS

Secondary electrons (SE) are weak and they can only escape if they are near the
surface and provides surface information. This is one reason why SEMs use relatively low
energy electrons to avoid SEs generated from deeper regions of the samples with high
energies to reach the surface. This could degrade the spatial resolution of the image. The are
emitted in all directions, but the SEM detector uses a reasonably strong field to gather them.

In addition to the elastic scattering, the beam electrons lose energy and transfer this energy in
various ways to the specimen atoms. This process produces useful imaging signals such as
secondary electrons and analytical signals such as x-rays.

Secondary electrons are defined as electrons with an energy of less than 50 eV, an arbitrary
choice, because most secondary electrons generated in the SEM are less than 5 eV. They are
relatively insensitive to atomic number, so there is little atomic number contrast. Secondary
electrons can be generated throughout the depth of primary electron penetration, but because
of their low energy their escape depth is shallow.

The secondary electron coefficient d is given by

d = nSE/nB = iSE/iB

wherenSE is the number of secondary electrons, nB is the number of beam electrons incident
on the sample, iSE is the secondary electron current and iB is the incident beam current.
BACKSCATTERED ELECTRONS

These are elastically scattered beam electrons that escape from the bulk specimen at
angles generally less than 90 degrees. That is, they enter the sample, they interact with the
specimen atoms, reverse their course, return to the surface, and escape. Though these
electrons change direction, they retain most of their energy.

The probability of elastic scattering increases strongly with atomic number Z, approximately
as Z2, and decreases as energy increases following a1/E2 dependence. This dependence of the
backscattered electron intensity on the atomic number, providing atomic number contrast in
the viewing screen, make them valuable in determining the composition of a sample. Low
atomic number elements such as carbon or sodium backscatter fewer electrons than gold or
lead and appear dark. The heavier elements appear bright. Backscattered electrons can
come from fairly deep within the sample interaction volume.

Backscattering is quantified by the backscatter coefficient h, which is defined as

h = nBSE/nB = iBSE/iB

wherenBSE is the number of backscattered electrons, nB is the number of beam electrons


incident on the sample, iBSE is the backscattered electron current and iB is the incident beam
current.
As shown above, there is a monotonic increase in the backscattering coefficient with atomic
number. This forms the basis for atomic number or compositional contrast mechanism in
SEM.

The slop of h versus Z is initially steep, but decreases with increasing Z, becoming very
shallow above Z = 50. This indicates that the atomic number contrast between the adjacent
pairs of elements is strong at low atomic numbers and weak at high atomic numbers.

The curve of h versus Z can be conveniently fit with an expression of the form:

h = -0.0254 + 0.016 Z 1.86 x 10-4 Z2 + 8.3 x 10-7 Z3

Maximum number of backscattered electrons are emitted along the surface normal if the
incident beam is parallel to the surface normal (0o tilt). If the specimen is tilted slightly, the
direction of the backscattered electrons can be controlled conveniently for better detector
positioning.

SEM Modes of image formation


1. Resolution mode: For high resolution images, dp must be as small as possible, while
maintaining a sufficient beam current for adequate visibility. M > 10,000 are possible
here.
2. High Current mode: For high image visibility and quality, large beam currents are
needed. This will produce a contrast between an image feature and the background
noise. Large current is also useful for x-ray microanalysis.
3. Low-voltage Mode: At low acceleration voltages ( 5 kV), the beam interaction with
the specimen is confined to regions very close to the surface. This will produce an
image which is rich in surface detail compared to those obtained at higher
accelerating voltage.

MICROANALYSIS IN ELECTRON MICROSCOPY

The electron beam generates both continuum and characteristic x-rays.

Bremsstrahlung or continuous x-rays

These are produced by the deceleration of the beam electrons by the Coulomb field of
the specimen atoms. Random nature of these interactions causes the electron to emit
photons of any amount of energy. The maximum energy photon corresponds to the
case where the incident electron looses all its energy. This is called the Duane-Hunt
limit and it is a measure of the incident beam energy.
The intensity of the x-ray continuum Icm at any given energy E is given by the
Kramers relation
Icm ~ ip|Z| (E0 E )/E

Where ip is the electron probe current, |Z| is the average atomic number based upon
mass fractions of the elemental constituents of the specimen, E0 is the incident energy
and E is the continuum photon energy

Characteristic X-rays

A characteristic x-ray is produced when an incident beam electron removes an inner


electron of the specimen atom and a higher shell electron moves into the vacancy
releasing the difference in energy.
The released energy can be transmitted to another outer shell electron ejecting it from
the atom as an electron with a specific kinetic energy. These electrons are called
Auger electrons.
The relative probability of de-excitation by characteristic x-ray emission and Auger
emission is described by the given by
K = number of K photons produced/number of K-shell ionizations.

The characteristic x-ray process is not favored for low atomic numbers K ~ 0.005
K ~ 0.5 for germanium and approaches unity for
heavier elements.

Electron Energy Levels


Except K, all other atomic shells are divided into subshells. The subshell structure
according to the quantum mechanical model of atoms is given below:

Depending upon the ionization state and the excited energy, excited atoms can be
placed in different excited energy states as shown below:

Some transitions are forbidden due to selection rules. For example, for copper K-
series, only two transitions are allowed resulting in K and K emissions.
The minimum energy required to remove an electron from a specific atomic shell is
called critical ionization energy or excitation potential or x-ray absorption edge. Each
shell or subshell of an atom requires a different amount of critical ionization energy
for electron removal. For example, a 20 keV electron beam can ionize the L and M
shells of Pt, but not the K shell. As the atomic number decreases, the ionization
energies also decrease. For x-ray microanalysis, SEM is operated at energies 2 or 3
times the critical ionization energies of the elements of interest.

Solid state semiconductor based detectors such as Li doped Si or high purity Ge


(HPGe) are commonly used. They work based on the electron-hole pair production in
the semiconductor by the absorption of x-ray photons.

Disadvantages:

1. Poor energy resolution (~130 eV with Si-Li detectors). Difficult to resolve


closely spaced lines
2. Poor detection of low energy photons, absorption by the detector window
Wavelength Dispersive Spectrometer (WDS)
Mostly used in electron probe microanalyzers (EPMA) the analytical version of
SEMs
WDS has superior energy resolutions, often better by a factor of 10.
WDS has high count rate capability
Employs a series of bent crystals to cover the range of wavelengths. Individual
wavelengths in each range is scanned by adjusting the angle 2 by rotating the crystal
and moving the detector.

Disadvantage:

All of the peaks must be scanned sequentially


Both EDS and WDS suffer primarily from the insufficient excitation of characteristic
radiation from the lighter elements.

The fluorescence yield is too low indicating that only a small fraction of the excitation events
leads to characteristic emission and the vast majority leads to Auger electron emissions. For
carbon (Z=6), only 0.5% excitations leads to characteristic x-ray emissions.

TRANSMISSION ELECTRON MICROSCOPY


Incident Backscattered
electrons electrons (SEM)
Characteristic X-ray (EDXS)
Secondary
electrons (SEM)

Elastically Scattered Transmitted Inelastically Scattered


electrons (TEM, HRTEM) electrons (TEM) electrons (TEM, EELS)

Specimen must be transparent for electron


ranging from atomic size to 1 m

Like in SEM, electrons transmitted through a thin slice of a sample suffer both elastic and
inelastic scatterings. It is the elastically scattered electrons that contribute to the transmitted
image. Inelastically scattered electrons provide information about the composition of the
sample.

If the sample is amorphous, then elastic scattering will be random in all possible angles. In
crystalline samples, the electron scattering follows the Braggs law generating diffracted
beams at selected 2hkl angles.

On the other hand, directly transmitted electron intensity depends on the sample thickness
and its density and the image formation is similar to the transmitted image in an optical
microscope. Since most of the directly transmitted electrons are along the geometric axis, a
suitable aperture can control the transmitted electrons or the Bragg scattered electrons. This
will allow us to selectively obtain a picture of the electron diffraction pattern from the
crystalline sample or a transmitted image.

Image Plane and Back Focal Planes


Image plane: All rays from a point in the object are brought back to a point in the image
. This is conjugate to the object plane or optically equivalent.

Back focal plane: All PARALLEL rays (whether parallel to the optic axis or not) are
brought to a focus in a plane at a position depending on their angle to the axis.
Rays parallel to the optic axis are focused on the axis and off-axis parallel rays
are focused off axis. This allows the formation of diffraction patterns in the
focal plane. Bright points or maxima corresponds points where the path
difference = n

To get very high magnifications M = v/u, keep the object close to the lens so that u is
small and M is large. Using multi-lens system allows to use the image (or
diffraction pattern at the back focal plane) of the first les as the object of the
second and so on, thus providing much higher magnification.
Use of appropriate apertures limit the collection angle of the lens which in turn
improves resolution of the image, depth of focus and field, image contrast etc.

The first two condenser lenses in TEM are adjusted to illuminate the specimen with a
parallel beam of electrons typically several micrometers across at reasonable
magnification.

In thermionic guns, the original crossover may be several tens of micrometers across
and this demagnified by an order of magnitude. For field emission guns, the
source size may less than the desired illumination area and the condenser
lenses will magnify the cross over.

SCANNING TRANSMISSION ELECTRON MICROSCOPY OR STEM.

A focused convergent beam may be used as a probe to obtain localized signals from the
specimen such as in selected area diffraction or microanalysis. However, this mode
would not provide a useful image of the specimen because convergence destroys the
parallelism and image contrast. To see an image in this case, we have to scan the beam
and this mode is called Scanning Transmission Electron Microscopy or STEM.
SELECTED AREA DIFFRACTION (SAD)

To conduct Selected Area Diffraction (SAD), we insert an aperture called SAD aperture
into the image plane of the objective plane. As shown below, This will collect electron
diffraction patterns from submicrometer regions within the sample. Instead of using a focused
beam on the sample, this allows the sample to be illuminated with a parallel beam, while
being able to select a small area for diffraction. Converging beams destroy the parallelism
and the spots in the pattern are not sharply defined but spread into disks.
Electron diffraction and Imaging
Electron beam

Braggs Law
Thin specimen 2d sin = n

Objective lens

Diffraction
Back focal plane
Single crystal Polycrystalline

Imaging

Image magnification Image

To see the DIFFRACTION pattern, we need to adjust the imaging system so that the back
focal plane of the objective lens acts as the object plane of the intermediate lens. Then the
diffraction pattern is projected onto the viewing screen

To obtain an IMAGE, the intermediate lens is so adjusted that the image plane of the
objective lens acts as the object plane of the intermediate lens.