TEM Exercise/answers:

Maybe as an introduction can you read (in your textbook) what TEM is used for?

TEM is a powerful characterisation method, able to characterize at the 0,1nm

scale chemistry (EDX and EELS techniques), structural defects in material
(nanograins, nanoprecipitates, dislocations, vacancies, …), to investigate
crystallographic structures, …

What is the special resolution in comparison with optical microscope?

The special resolution is linked with the wavelength : physically, we cannot see
objects smaller that .
In an optical microscope, the photon wavelength lambda ranges from 0,4 to 0,8
µm (visible light), therefore we cannot see objects smaller than 0,5 µm, even if
the lenses are perfect! That’s why there is no point to magnify objects more
than 1000 times in an Optical microscope.

In an electron microscope, the wavelength is associated with the acceleration

voltage. At 200kV, electrons have 200eV energy, then 200kV= 0, 0025nm. The
higher the voltage, the lower the camera lens.
So if we are able to build a perfect TEM, i.e. perfect electromagnetic lenses, we
could see easily atoms. Up to 15 years ago, it was very difficult? Then a small
company decided to live with “the quality of lenses we had” l, but add a new set,
that could be tuned to correct the first lenses. These microscopes are called
corrected TEM, they are very expensive, but allow great images!
For example, hardening precipitate in Al alloy: the contrast here corresponds to
atoms chemical composition: the brighter the heavier the atomic number Z.

It is important to remember that

what you see here, is the
projection of a volume. So the
sample was tilted so that all atoms
are aligned on the top of each
other. Because we see squares in
the aluminium, the sample normal is
<100>
(from Aberration-corrected HAADF-
STEM investigations of precipitate
structures in Al–Mg–Si alloys with low
Cu additions

Takeshi Saito, Calin Daniel Marioara,

Sigmund Jarle Andersen, Williams
Lefebvre, R. Holmestad, 2014, Material
sciences.
The drawback of TEM is that we need small and thin sample, what is the thickness?
See p 68 of your class document: bellow 100nm. Today, we are happy with 30nm
sample, since grains are becoming very small!

1) Explain in a TEM the trajectory of electrons after they interact with the specimen.

Here I want you to explain the different interactions between mater and electrons. It is
in the document you were given for the characterization class.
If you look in your text book, SEM section, you have p10:

In the TEM we work with higher Energy (from 80kV to 400kV, even 1 000KV,
but classically 200kV), but all this interactions happen. But because of the
geometry of the microscope (in transmission), we will be more interested in what
“go through” the sample p67:
 Among all this interactions, there is one, which is elastic (the energy of electron_ i.e.
the wave length, is conserved): diffraction.

Recall Bragg’s law. What can you say about theta values, what can you say about the
orientation of diffracting planes versus the incident electron beam?
2dhkl sin= (n)
dhk is the inter reticular spacing, about 0,2nm in metals,  is 0,0025nm, that
means sin is very small, so sin = The plane that diffracts are // to the
electron beam!

Incident beam
All vertical planes are diffracting!

The vertical ones I draw, but also for example the ones that are parallel of the
paper or your computer screen.
That needs to be clear for you. Moreover, the diffraction vector is // to the
normal of the diffracting plane. (see patterns bellow)
For example, If I have a Cubic material, oriented with [001] axis vertical, I
should see the diffraction of [100] and [010] planes but also [110]
Then, by symetry of the crystal :
2) What happen with the objective lens?
After the electron have diffracted, they reach the Objective length (OL). What is there
trajectory up to the image plane? remember your optic class several years ago!

specimen A B
t transmitted beam from A

d diffracted beam from A

OL

BFP

IP (image plane)

B’ A’

PL

Screen

Remember, all beams are deviated by

the OL, except the ones that go
through the optic centre of the lens.
Because the diffracted beam in A is
going through the optic centre, it is
not deviated. As it was emitted in A, it
should also converge into A’.
The intersection point of diffracting
beam d from A will be the focus point
of all beams // to this one. So the
diffracting beam in B, // to the one in
A follow this trajectory.:
For those who had the practice, what do we see on the screen? What is the role of the
(intermediate) projective length?

PLPL

(real transmitted beam is highlighted)

BF is the back focal plane, IP the Image Plane, PL is the projective lens, and the
screen is the observation screen.

On the screen, we will see what was in the object plane of the projective lens. If
it is tuned to be the Image plane of the objective lens, we will see an image. But
because it is electromagnetic, the tuning can be changed, and the object plane
can be chosen to be the back focal plane (where we see the diffraction) of the
Objective lens, therefore we can see the diffraction, and record it, as was done
for fig.1.
3) We are studying a TiAl alloy, constituted of a single ordered L10 cfc phase, TiAl,
a= 3.98 A.

Ti

Al

L=70cm,
fig 1: Diffraction of TiAl, HV=200kV (lambda = 0.0025nm)

(fig 1 is the negative reproduction at scale 1 of a diffraction pattern of TiAl, oriented in a

preferential direction, because you can see a motif, taken using a 200kV microscope)

Calculate the structure factor for FCC than for TiAl

- What is number of atom to describe FCC cell? What is there position?

- What is number of atom to describe TiAl FCC cell? What is there position with
composition?
In a FCC cell, we have 4 atoms with no chemical In TiAl cell, we have 4 atoms with
specification: chemical ordering:
- 1: (0,0,0) - 1Ti: (0,0,0)
- 2: (0, 1/2, 1/2) - 2 Al: (0, 1/2, 1/2)
- 3: (1/2,1/2,0) - 3 Ti: (1/2,1/2,0)
- 4: (1/2,0,1/2 - 4 Al: (1/2,0,1/2

We remind that the diffracted wave is:

With F, the structure factor: where f is the diffusion factor

of element i
Calculation for FCC: (I do my best for this equation, but my equation editor does not work)

So, we have 4 atoms -> F=∑ (1->4) fi e (i2π K.rj), with K = (h,k,l) and rj the atoms positions

So we have:
F= f x (e (i2π (0xh+0xk+0xl) + e (i2π (0xh+1/2xk+1/2xl) + e (i2π (1/2xh+1/2xk+0xl) + e (i2π
(1/2xh+0xk+1/2xl))

F= f x (1 + e (iπ (k+l) + e (iπ (h+k) + e (iπ (h+l))

Now if h,k,l are all even or odd :

F= f x (1+1+1+1) = 4f
Now if h,k,l have different oddity (?) :

F= f x (1 -1 +1-1) =0
So,in FCC, we cannot see 100, 110, … diffraction dots, but 200, 220, 111, ….

Calculation for TiAl :

So, we have 4 atoms -> F=∑ (1->4) fi e (i2π K.rj), with K = (h,k,l) and rj the atoms positions

So we have:
F= fTi x e (i2π (0xh+0xk+0xl) + fAl x e (i2π (0xh+1/2xk+1/2xl)
+ fTi x e (i2π (1/2xh+1/2xk+0xl) + fAl x e (i2π (1/2xh+0xk+1/2xl))

F= fTi x (1 + e (iπ (h+k)) + fAl x (e (iπ (k+l) + e (iπ (h+l)))

Now if h,k,l are all even or odd :

F= fTi x (1+1) + fAl x (1+1) = 2(fTi + fAl)

Now if h,k,l have different oddity (?) :

h and k different oddity: F= fTi x (1-1) + fAl x (1-1) =0

h and k same oddity: F= fTi x (1+1) + fAl x (-1-1) =2(fTi - fAl)

So,in TiAl, we cannot see 100, 010, … diffraction dots, but 001, 220, 111, ….

Now we will work on the diffraction figure, given fig 1.

Explain what was done to record that picture.

(It is link to the Projective Lens (which is also intermediate…))

We tuned the current in the intermediate lens so that we see se diffraction on

the screen, and we recorded it

Index the diffraction diagram based on calculation or identification, first considering only
the big dots.
1) Calculation :
Decide which point is the centre, and take it as a reference
Big small centre

You should have in your text book the following relation: lamdda/dhkl = R/L (see p 80)

Where lambda is the electron wave length (lambda = 0.0025nm), L=70cm camera length, d hkl
the interreticular spacing and R the distance between spots.

Express dhkl as a function of the lattice parameter in a cubic material.

Here you can define two R distances, R1 and R2

Measure R1 and R2 in cm, directly on the image (for better accuracy, measure between 4 or 5
spots, and divide by the nb of intervals.
From the value of R1 and R2, you can find d hkl 1 and dhkl 2, and then which hkl plan the spots
correspond to.

R1 = 0,875 cm (I measured 4
distances then divided by 4)
 /dhkl = R/L -> d1hkl =  L/R1
d1hkl = 0,2 nm ->a/2
-> {hkl} = {200}

R2 = 0,76 cm (I measured 6 distances

then divided by 6)
 /dhkl = R/L -> d1hkl =  L/R1
d1hkl = 0,23 nm ->a/√3
Rq : we know the [002] direction (it is the ordering
-> {hkl} = {111} direction), but <111> can be any permutation

Then you can find in what direction the grain was oriented before the image was taken.
You have to make the cross product of the two in plane directions,
[002]^[111]= [-220]. So the crystal was oriented with a (110) type direction // to
the e-beam. This (110) or exact [-220] direction is called the zone axis. The
sample was rotated so that (110) type orientation was // to the e-beam.
What are the small dots corresponding to?
The small dots correspond to the [001] diffraction dot, which is not forbidden
due to the chemistry of TiAl, consisting into alternating Ti and Al plane in the.

So the diffraction pattern tells us that there is a chemical ordering in the [001]
direction of the FCC crystal (it does not tell us which element though…)

2) Identification:
What is the reciprocal lattice of a FCC crystal?
BCC

Draw this lattice in 3D. Diffraction patterns

are intersection of the reciprocal space and
the Ewald sphere. See p74 of the class
document
Ewald sphere

Nods of the reciprocal lattice (elongated due

to the thin sample

What would you see if the electrons are arriving // to the 001 direction of the crystal, draw the
pattern, and respectively // to the 111 direction of the crystal, draw the pattern,
Finally respectively // to the 110 direction of the crystal, draw the pattern,

(the central atom is not on (111) plane)

e-beam // [001] e-beam // [111] e-beam // [110]
Rq : Now we know we have a FCC, we apply the extinction rules for indexation
Conclude on the orientation of the crystal before the image was taken.
In the data, we can recognise a centered square, which mean opur electron are
coming from [110] direction.

Experimental data Identification of a centered square

Calculation method
Comparison with patterns

4) Two images were taken: explain what you see. (like the diffraction pattern, these are
negatives of pictures, what is white was black on the screen)
This was after the specimen was plastically deformed if 2%.
Can you guess first if we expect a ductile or a brittle behaviour for this TiAl material?
FCC materials are ductile: they have 12 glide systems
4 dense planes {111}: (111), (11-1), (1-11),
(-111),
And in each plane, 3 glide directions
for dislocations:
For example, in (111) plane, dislocations
can glide in [1-10], [10-1] and [01-1]

In TiAl fcc ordered structure, there is also have 4 dense planes {111}: (111), (11-
1), (1-11), (-111),
But in each plane, only one glide direction
is available for dislocations: chemical
ordering prevents atoms from different
species to be interchanged. So we can
move an Ti atom into an Ti position but not
a Al position.
So there is only 4 glide systems in TiAl,
not enough for polycrystal plastic
deformation (5 independent systems are
needed for co-deformation of different
grains.)

->So TiAl material will be brittle, and it will need other ways to deform
plastically.
(these ordered structure of metals are called “intermetallics”, and they are
usually all very hard and brittle materials)

Let’s look at images now….

X14000
-What are the curved lines? why do they have ends?
The curved lines are dislocations. They are slightly bended, this means they are
under stress.
Dislocations have no terminations: they either terminate on grain boundaries,
surfaces, or they make loops, but they cannot just stop…. Here we have to
remember that what we see is the projection of a volume. Dislocations are
probably inclined in the volume, and we see their projection. The two “ends” are
intersections with the sample surfaces….

Rq: It’s difficult to know which is the intersection with the top or the bottom,
but it is feasable.

On this image, we see a lot of curved dislocation

emitted from this area. To me, it looks like the
result of dislocation emission by a franck-read
source.
If you want to remember how a franck read
source work,
1) Ask me
2) Look at this website, collecting the work
of from simap researchers, and modelling
of Marc Fivel :
http://www.numodis.fr/tridis/frank.html
 - What does this contrast correspond to? What is the straight domain?
This “zebra” contrast correspond to a grain
boundary: The transmitted intensity in the TEM is a
“sinus” function of the thickness: as a result, for some
thicknesses, intensity becomes 0. That’s why we have
alternating white and black contrast. We see this near
the edge of the sample, where usually the thickness
vary, but also at grain boundaries, where the incline
boundary correspond to a change in thickness in one
grain

This straight domain is a twin: twinning is a plastic deformation mechanism, that

can be activate when enough “regular” dislocations cannot move to accommodate
plastic deformation, which is the case in TiAl.
Twinning occurs along a {111} plane type, with partial dislocations, that’s why it is
very straight: what we see is the trace of a {111} plane.

{111]