Techniques of Materials Characterization

Prof. Shibayan Roy

Materials Science Center
Indian Institute of Technology - Kharagpur

Lecture – 25
Application of Electron Diffraction

Welcome everyone to this NPTEL online certification course on techniques of materials

characterization. And we are in module 5 that is week 5 and we were discussing about
transmission electron microscopy. So far in the last two weeks, we have covered the
imaging, different type of imaging modes, different sources of contrast genera tion in
transmission electron microscope.

And of course, then we were discussing about electron diffraction little over a week. And
we have discussed about first the sources of diffraction, how it happens, Bragg's law,
reciprocal lattice, Ewald sphere construction. And then we also have seen different
aspects of solving an index diffraction pattern, so indexing electron diffraction pattern,
what we need to know in order to solve an electron diffraction pattern or what the
information that we can derive out of this electron diffraction pattern and so on.

So, in the last class we had a very lengthy discussion about how to index exact procedure
and how to index this electron diffraction patterns. And today we will be discussing
about the application of electron diffraction pattern. Though I have written application of
electron diffraction pattern, but in some sense these are general application of
transmission electron microscope for different type of metallurgical materials problems.

Of course, the possibilities are endless. So, you can do depending on your nature of a
problem, the transmission electron microscope can come very handy and you can use it
for various purposes. Here I just try to list some very basic application areas where
transmission electron microscope is very popular and most often they are used for these
kinds of purposes. So, we will of course continue.
(Refer Slide Time: 02:15)
We will start with the importance of electron diffraction pattern. Then we will take some
few specific examples like dark field, imaging, phase identification, orientation
determination and finally we will talk about one very special technique that is called
dislocation contrast. So, dislocation contrast is a very important part of TEM both for
imaging as well as for the diffraction or it is related to diffraction only this contrast
generation mechanism.

But little different than the typical diffraction contrast that we see in dark field mode.
And we will see how it can be useful for the study of dislocation, something to do with a
dislocation, we will discuss about that.
(Refer Slide Time: 03:00)
So, first of all of course the importance of indexing of diffraction pattern. Here we have
named a few of the areas, but as I said the possibilities are endless. And you can use it as
when you require the electron diffraction pattern or as a general or more generally the
transmission electron microscope. So, this already we discussed to accurately measure
the camera constant using polycrystalline gold film.

So if you do that index, if you index the diffraction pattern you can know this camera
constant and from there again further you can calibrate the machine. And you can further
go ahead and do this indexing for any other kind of diffraction pattern. Of course, you
can also use this diffraction patterns for imaging diffraction contrast mode in dark field
imaging, we will discuss that. And these two are basically almost related.

This to identify an unknown material from lattice parameters and symmetry of

diffraction pattern. So, to identify phase identification by electron diffraction pattern and
also from there if you know the phase then you can possibly get interplanar spacing for
lattice parameters for any known or unknown materials. Also, you can use it for
determining the exact orientation of a material, we will discuss about that. And an
extension of this is to determine the habit plane or epitaxy.

We have discussed in the last class how this electron diffraction pattern can be very
helpful in determining the change in the single crystal to polycrystal and then it can help
you to identify the nature of epitaxy, nature of the habit plane and orientation
relationship between various phases. And finally, of course to produce defect contrast
that is g cross b contrast that is what we call and determine the dislocation Burgers
vector. This is something that is very unique and we will discuss about this today.
(Refer Slide Time: 04:58)
So, first thing of course dark field imaging and in dark field imaging even know that
either we can use the entire scattered beam or we can selectively use the diffracted beam
and then try to image certain features of exact orientation, we can determine their
orientation as well. For example, if you see this structure, so these are the bright field
images and correspondingly these are the dark field images.

But some speciality is this dark field images here we use different part of the diffracted
beam corresponding to different spots corresponding, some cases the beams are coming
from one particular atomic plane we are choosing let us say first order beam of 111
plane, sometimes we can choose the first order beam from 200 players so on and so
forth; the possibilities are endless. And we can get these different kinds of dark field
images.
(Refer Slide Time: 05:48)
So, the way we do it we already discussed and that time I told that we can possibly come
back to this one, this method of dark field imaging in transmission electron microscope
after we discuss the electron diffraction pattern, this will make much more sense. So,
exactly the same thing. Now, as we all know that diffraction, here dark field imaging can
be done by using a suitable aperture.

You can bring that aperture and you can either close all the diffracted beam , you can just
allow the direct beam, in that case you are getting a bright field image and then you can
try to bring the aperture or tilt the beam whatever. If you are on axis, off axis, dark field
depends on that. But let us say we are on off axis dark field mode, so what we can do is
that we can bring that same aperture, now we can close the direct beam completely and
allow a selected diffracted beam.

And this selection usually is done by seeing the diffraction pattern. So that means you
must identify the diffraction pattern, you must take an SAD pattern, let us say SAD
pattern or a complete ring pattern whatever it is, let us say it is a single crystal or it is an
SAD pattern, so we get a spot pattern here. And what we do is that we first just allow the
direct dream for the bright field image and then we tend to select one of the diffracted
beams.

So, we tend to select the beam corresponding to one of these spots, either we can choose
this one or certain cases we can also try to choose multiple number of diffracted beams
so on and so forth. So, the possibilities are endless. So in modern days, it is all software
related. So, basically you see the diffraction pattern, you take your cursor, you select that
beam, and automatically the objective aperture will go and select that part of the
diffracted beam.

It will stop the direct beam and it will just allow that part of the diffracted beam or you
can allow multiple diffracted beams whatever, depends on the aperture size, depends on
your choice.
(Refer Slide Time: 07:45)

If you do that, this also we have discussed, then this kind of beautiful things you can do.
You have this bright field image. You have this corresponding diffraction pattern.
Basically, it is a spotty pattern; it is not a spot pattern, neither it is a ring pattern. So
spotty pattern that is because of the orientation of many crystallites which are here
contributing to this ring.

So, you can correspondingly choose some different rings here and from there you can
identify these beams or these grains out here. So, if you see that you are in case one case
you are taking this green dot, corresponding to this green dot here you are imaging one
single grain and then if you choose some other dot here some other diffracted beam, then
you are able to selectively see this grain.

So, not only you can image them, you can also know exactly which part of the
diffraction pattern is contributed by which grain that means we will come to that, you
can basically identify the orientation of these grains as well in the microstructure. So,
that is a very good nice thing that you can do by taking advantage of this electron
diffraction pattern and then use it for imaging from this diffraction contrast mode .
(Refer Slide Time: 09:03)

Of course, you can also do phase identification from selected area diffraction that is
something that we were discussing. So, if you have let us say, I have taken an example
of silicon. So, silicon is generally used as a wafer, silicon wafer for the electronic
industry, packaging industry, semiconductor industry and many cases they tend to dope
it or otherwise it may have some impurities and that may change the lattice parameter
from the standard one.

And by solving the diffraction pattern, you can actually identify the d spacing. So, what
you are doing you know lambda, you know sine theta and you are trying to find out the d
by looking at this pattern. So you know that you need to know the your material a prior,
you need to know the chemical identity of your material a priori. So you know it is
silicon and you know lambda, you know sine theta, and what you do?

You know the camera constant, all of these things you know and you then solve this
diffraction pattern. You measure the same thing r 1, r 2 all of these and from there you
accurately measure this d spacing and from there either you can identify the material or
if it is known material you can get the lattice parameter.
So, this this is a most possibly most common example. Of course, you have to be careful
about all the previous class whatever the precautionary measures that we have discussed,
you must be aware of all of these things.
(Refer Slide Time: 10:27)

Life becomes of course a little more complicated when you do not know anything about
the material or either its chemical identity nor its crystallography nothing. Then solving
this identity of this material new materials or to know about their crystal structure is
extremely difficult. I just tried to show here one example and this is a very typical
example, many of you may have faced this one.

So, whenever you are trying to bond a ceramic with a metal, so they do not go and
particularly if it is for high temperature application. For example, this is YSZ yttria
stabilized zirconia, you are trying to melt it or trying to bond it with steel. With a steel
substrate you are trying to put a ceramic coating usually this is why if there is a thermal
barrier coating improves the thermal capability of any components, most likely it is, I do
not know exactly, but most likely it looks like it is a turbine component most likely.

So, you want to increase the temperature capability of this component of the steel and for
that you want to coat it, but the problem is that this metallic part and the ceramic part
they have completely different thermal expansion coefficient. So, if there is a thermal
cycle that goes on this may very easily undergo a thermal shock and this too because of
the difference in thermal expansion coefficient, the ceramic layer, the coating can very
easily peel off that can disintegrate from the metal.
So, because there is not really a very nice bonding or close bonding, tight bonding
formed between the ceramic and the metal part. In order to negotiate this problem what
people used to do is that they used to put another coating which is known as bond coats.
So, these bond coats have intermediate thermal expansion coefficient between the metals
one side and ceramic one side.

And in order to make it even better what they do is that they try to grow from this
metallic this bond coat, there is another intermediate layer which is in-situ grown and it
is known as the thermally grown oxide layer. So here once side thermally grown oxide
layer is shown, which is basically titanium and titanium where the oxygen diffuse s and it
reacts with oxygen and forms this titanium oxide.

But the point is that here this titanium oxide phase is nonstoichiometric and its
composition, its crystal structure, everything changes over this length. So, in order to
determine what exactly is the crystal structure here or their chemical nature or the phase,
it is extremely difficult because you do not have any guidelines. You do not know, you
can have this chemical identity check first.

You know it is titanium it is oxygen, but it is nonstoichiometric and then to solve their
diffraction pattern and to get an idea about the exact phase stoichiometry and to get the
crystal structure it is really a tough job. But of course, people do that and this gives
fantastic result, but this is one example of identifying the phases.
(Refer Slide Time: 13:31)
Next orientation determination by electron diffraction. Of course, orientation, what is
orientation, what is called crystallographic orientation and all that is a subject in itself ,
we are not going into this. Roughly what we can call is it is if you have a specimen a
bulk specimen of material or a process, if you have this specimen axis that is what we
call it the specimen axis here.

So, let us say you have a rectangular bar of this, a bar of rectangular cross section. So,
there are three orthogonal directions. You have this X, Y and Z directions here which are
if it is a rolled plate typically called rolling direction, normal direction and transverse
direction and then the crystallography direction. So, you have let us say this is a cube
crystal, this is a let us say a unit cell, so, you have certain crystallographic directions.

Now, what we try to find out is that which one, what is the direction that is lying along
this normal direction or Z direction and what is the direction of that is lying along this
RD or rolling direction or X direction. So, that interrelation is basically the orientation,
roughly you can call it is the orientation. The interrelation between these
crystallographic directions and this bulk specimen direction this is the orientation.

Now, this orientation determination by electron diffraction is very useful here because
you know by virtue of electron diffraction, basically only the planes which are parallel to
the specimen normal or in other words the planes zone axis is always normal or always
parallel to the specimen axis. That means if you understand this that means your hkl, if
you imagine this is the zone axis this is automatically parallel to normal direction.
So, if you take an electron diffraction pattern, you determine the zone axis the way we
discussed in last class from Kikuchi diffraction pattern or normal selected area
diffraction pattern, you determine the zone axis and by that what you can get is at least
one direction, you can know which is parallel to the specimen normal, you can determine
one. Now, what happens is if this is a rectangular piece and rectangular cross-section, so
you have two important directions here.

And imagine that this is a circular cross section, in that case both RD, TD all of them are
same, you have only one ND direction that is important. In that case, you can very safely
determine the crystallographic orientation of this material and you can by tilting or by
other means by using crystallography you can of course determine this RD that is
direction parallel to rolling direction all of that.

But basically, you can determine the direction or determine the orientation of this
material simply by electron diffraction and not to mention the advantage of thi s is that
you can determine this in a very small length scale. That means in a microstructure you
want to know the orientation of a particular phase, then you can do that by using a
selected area diffraction pattern.

So, you can choose an aperture which is exactly of the size or even smaller than the size
of that particular feature and you can identify the orientation, what is the zone axis and
what is the orientation of that feature. And that is exactly one example I have shown that
this is one type of precipitate which is here and you can see that the precipitate has
certain interfaces, which again looks like faceted interfaces that is what we call it.

Faceted interface and that means these interfaces have a particular orientation. So, by
solving this diffraction pattern not only you know the zone axis, but also you can
identify these different phases here, how this precipitate basically grow, what angle it
makes. This is essentially like a single crystal. So, this single crystal you know that this
is possibly the 111 plane, this is 110 plane and so on and between their angles and all of
this.
You can determine how the precipitate grows, what are the facets, what is their
orientation everything you can identify just by simply solving this selected area
diffraction patterns.
(Refer Slide Time: 17:37)

One step further from there, you can obviously determine the orientation relationship , we
have discussed about that in the context of titanium 6 aluminum 4 vanadium where you
have this alpha phase, hcp alpha phase next to BCC beta phase and by taking either a
selected area diffraction pattern from individual phases with the same zone axis and then
you can superimpose them.

And without changing the zone axis basically you can take a selected area diffraction
from this and from this and then you can superimpose, you can try to find out what is the
relative direction, which directions are parallel between these two phases and how much
relative rotation is needed and all such things and that is the way you can find out or
otherwise the way we did it in the last class.

You can take a selected area diffraction pattern from this interface region, where both
the phases will contribute. And there also by solving for both phases, you can identify
the orientation relationship between these two phases.
(Refer Slide Time: 18:33)
And at times as I said it comes very handy because of the inherent scale length scale at
which this electron diffraction patterns are determined by selected area diffraction. So,
for example, this is a steel specimen and within the steel specimen, you have many
different types of precipitates. So, steels usually have a very complex microstructure
where you have like carbides or nitrides, microalloying agents, microalloying elements
which forms various type of precipitates.

So, now if you want to know the orientation of those precipitates and more importantly if
you want to know the orientation relationship of those precipitate with respect to the
matrix or the orientation relationship between them, what you can do you can take again
selected area diffraction pattern from various phases, different phases, and then try to
solve it and from there you can determine the orientation relationship. So, that is how
you are using this electron diffraction for solving various type of materials problems.
(Refer Slide Time: 19:34)
The last part of it with that we will also close our discussion on transmission electron
microscope is the observation of dislocations. Now, dislocations I am not discussing
much. I hope you already have an idea about what is called dislocations. So, dislocations
basically the way we can visualize them at least for edge dislocations is a missing atomic
plane. So, if you look at here these are atomic planes and we can imagine that this
atomic plane continues up to here and after that it misses out.

What happens is that these dislocations are invisible depends; invisible or visible
depends on the bright field or dark field whatever field we are seeing or they are
invisible or exhibit very weak contrast in bright-field mode if g cross b where g is the
diffraction vector, remember we discussed about the diffraction vector that is the zone
axis and b is the Burgers vector for dislocation.

Again, I am not going into what is Burgers vector and all. Burgers vector basically
represents the dislocation. It gives the amount or magnitude of that dislocation and
sometimes it is direction as well, depends on the edge dislocation and screw dislocation.
So, Burgers vector defines a dislocation. Burgers vector and line vector, these two
things, line vector is basically the direction of the dislocation; these two defines a
dislocation.

So, Burgers vector determination is very important in the field of dislocation. People
who study dislocations, they want to know Burgers vector all the time. Now, this is the
condition where if g cross b = 0 that means those dislocations are diffracting. Now, how
this happens? So, as I said that dislocations are defects, line defects basically, where an
atomic plane is missing. So, as this schematic is showing and really it happens.

We can see it in high resolution microscope, I will show you one such image. Then the
atomic planes are bend particularly this place which is called the core of the dislocation.
So, near to the core of the dislocation, the atomic planes are kind of bent and if you go
further away this bending is reduced. So, this is a very localized effect this atomic
bending, a clear bending of atomic planes.

Now, what happens is because of the bending the d spacing changes there atomic planes.
So, whatever is the d spacing between these atomic planes here somewhere further away
from the dislocation that is definitely changes somewhere very close to the dislocation
core. Most likely it increases here because an atomic plane is missing and that will affect
the diffraction phenomena because if you remember according to Bragg's law diffraction
strongly depends on the interatomic spacing.

So, if your lambda is constant, your sine theta is constant, if you change the d or rather
the lambda is constant if you change the d, your sine theta is going to change. So, some
things, some crystal; now if you imagine that some crystal is oriented on certain planes if
this is let us say 111 plane, then if you have the zone axis such that now 111 planes are
diffracting, they are satisfying the diffraction condition close to the dislocation or near to
the core of the dislocation since the d spacing is different.

That means those are not satisfying the diffraction condition and these are not in
diffracted or these will not produce any intensity for the diffracted beam or vice versa on
the other way around you can imagine that if some parts are not diffracting or its zone
axis is such that these are not diffracting, the rest of other planes are not diffracting close
to the dislocation that may satisfy the diffraction condition and for that the g cross b = 0.

If g cross b = 0 that means those dislocations are in diffraction condition and dislocations
will diffract. So, if they diffract strongly, then what will happen is that if you just now
capture the direct beam for bright-field image those regions from the diffracted regions
or from the dislocation regions, now there is a strong diffraction effect. So, those areas
there will be a loss in the intensity of the direct beam.
So, those areas will appear very dark line or black line in bright -field mode and vice
versa correspondingly it will appear a bright line in dark-field image. If you choose that
particular diffracted beam from dislocations, then in the dark-field mode, it will appear
like a bright image. So, that is how dislocations can be imaged using this dislocation
contrast under transmission electron microscope.
(Refer Slide Time: 24:30)

And that is what is very important with people who works with dislocations, for them
seeing the dislocations is, more than seeing using this diffraction contrast you can
determine because you know the g, you know the diffraction vector and from there you
can identify the Burgers vector. So, this is another advantage that not only you can
visualize these dislocations here.

But since these entire phenomena is extremely crystallographic it is related to the

crystallography, so you can determine the Burgers vector of the dislocations as well. And
that is a big thing in the study of dislocation. So, if you look at these three different
cases, so here you change the g vector and you are basically seeing, g vector is in both of
them are 111 family, but exactly not 111, so different particular planes the g different
direction the zone axes.

You are basically imaging different type of dislocations here. If you change the zone
axis, different dislocations and now dislocations are forming on different atomic planes
and direction, so with different Burgers vector. So, now what happens is you are able to
image the dislocations at different zone axis, not only that since you know the zone axis
what you can determine is the Burgers vector of those different dislocations.
(Refer Slide Time: 25:53)

This is extremely important in the study of dislocation field. Whichever way people
produce dislocation, dislocations are important like if you deform a material, you will
get dislocations, even sometimes I used to get students who are coming with thin films
and all, there you have misfit dislocations for example. One such example I have shown,
I will come to that, but more than anywhere you can use this dislocation contrast and you
can find out the dislocation.

So, dislocation contrast in TEM is possibly the only way to directly see the dislocations
and directly you can determine the Burgers vector. All other methods of determining
Burgers vector of dislocations is indirect, only in the TEM possibly you are getting that
and you will be able to see the dislocations and you will be able to get their Burgers
vector so that TEM is very important.

In fact, in 50s when this condition was determined and people started getting the
dislocation image, so many of the theories before the dislocations, most of the theory of
dislocations were derived on paper and after 50s when transmission electron microscope
becomes powerful it was able to see the dislocations and determine Burgers vector, then
those theories were proved right.
And you can go ahead with one step further with dislocation you can determine the
nature of something called stacking faults. And stacking faults is again a combination, it
is a dislocation phenomenon. Stacking faults are basically regions where the stacking
sequence change and both sides of stacking faults we call something like call partial
dislocation, they are bounded by partial dislocation.

So, you can determine those partials, you can see those dislocations, so they also
produce pretty much similar dislocation contrast. From there you can find out if you
know zone axis you can know the nature of this stacking fault. Even you can see under
the deformation condition, when we deform a material very high extent these
dislocations form some kind of structure which we call sub-structure formation.

And then there are some metallurgical processes like dynamic recovery, dynamic
recrystallization, and so on. And those processes form typical dislocation structures,
which again you can see it in transmission electron microscope for that and if you choose
your zone axis properly, you can even identify the nature of the dislocations there.
Finally, this is one nice example what I was telling that you can determine the Burgers
vector in a high-resolution image.

Where you are actually visualizing, you are actually imaging the atomic columns, you
can try to find out the missing atomic plane and you can actually find out if you look at
here the atomic planes are really bent. So, there is a dislocation which is present here and
this is for typical semiconducting material gallium arsenide and gallium antimonide. And
here just by drawing this Burgers circuit, you can determine the Burgers vector of this
dislocation.

This is called a misfit dislocation. So, this is the implication, one of the very big
implication of transmission electron microscope in the study of dislocation. So, with this,
we are closing our discussion about transmission electron microscope here and in the
next class or next week onwards, we will be moving to another really important electr on
microscopy technique that is scanning electron microscope. And till then, goodbye .