Electron Diffraction

At the end of this lecture you should be able to

(1) index SAED patterns in case the cell parameters

are already known
(2) determine the possible space groups from SAED
patterns

(3) determine possible point groups from CBED

patterns

Combine (2) and (3) to find the space group.

Reflections: what do they represent?
What is their origin? What information
can they give us?
 Constructive vs. destructive interference
reflection – no reflection

position  distances between the planes (d-values)

intensity  occupation in the planes
both symmetry of the structure
Crystalline or Single
amorphous? phase?

Orientation
Targeted
crystals/film
phase?
?

Crystal Domain
parameters? formation?
Selected Area Electron
Diffraction
SAED
 b
a

One atom type A

b>a
a=3 Å
b=5 Å
 b
a (100) 000

One atom type A 100

b>a
a=3 Å
b=5 Å
 b
a (100) 000
1/3Å
One atom type A 100

b>a
a=3 Å
b=5 Å
 b
a (100)
a*

One atom type A 100

b>a
a=3 Å
b=5 Å
 (010)

b
a

One atom type A

b>a
a=3 Å
b=5 Å
 (010)

b
a 010

One atom type A

b>a
a=3 Å
b=5 Å
 (010)

b
a 010
1/5Å

One atom type A

b>a
a=3 Å
b=5 Å
 (010)

b
a b* 010

One atom type A

b>a
a=3 Å
b=5 Å
 [001]

b
a b* 010
a*

One atom type A 100

b>a a*>b*
a=3 Å
b=5 Å
 [001]

b
a 000 b* 010
a*

One atom type A 100

b>a a*>b*
a=3 Å Central reflection
b=5 Å is always 000.
 [001]

b
a 010

One atom type A 100

a=3 Å
b=5 Å
 [001]

b
a 010
1/5Å
1/3Å
One atom type A 100

a=3 Å
b=5 Å
Indices all other reflections:
vector addition

[001]

010
020

110 120
100
200 210
Experimentally: the other way around:

[001]

1/5Å 010

1/3Å *
100
 *How?
Make a list of all reflections with hkl and their d-values.

• use Excel to make the list yourself

• use free software like Powdercell
• ...

d hkl
7.68 001
5.64 010
5.46 100
4.55 011
4.45 101
3.92 110
... ...
 Zone-index: [001]
obtained by vector multiplication.

100100
010010

0 0 0 1 1 0
010 1 0 0 0 0 1
0*0-0*1 0*0-1*0 1*1-0*0
100
[001]

Circle ACW around 000.

 [001]

[001]
-
110
010

100 110
(100)

-
(110) (110)
(010)
 Exercise:
index the given patterns taken
from a CaF2 mineral
 CaF2
cubic
a=5.46 Å
-
Fm3m

a
a

c c
b
b
 You need this table made for CaF2

h k l d I F
1 1 1 3.15349 83.73 61.89
2 0 0 2.731 0.11 3.07
2 2 0 1.93111 100 96.55
3 1 1 1.64685 31.44 46.49
2 2 2 1.57674 0.2 6.81
4 0 0 1.3655 12.69 74.25
3 3 1 1.25307 11.35 38.65
4 2 0 1.22134 0.54 8.67
4 2 2 1.11493 23.75 61.87
5 1 1 1.05116 6.88 34.2
3 3 3 1.05116 2.29 34.2
 We are going to index these patterns.
They are obtained by tilting around the diagonal row.

(Online version:
working page can
be found at the
end.)
 We are going to index these patterns.
They are obtained by tilting around the diagonal row.

(Online version:
workpage can be
found at the end.)
 (Online version:
workpage can be
found at the end.)

Start with easiest:

highest symmetry or smallest interreflection distances
= usually lower zone indices (“main zones”)
Why go for smaller interreflection distances?
=higher d = less choices
h k l d I F
1 1 1 3.15349 83.73 61.89
2 0 0 2.731 0.11 3.07
2 2 0 1.93111 100 96.55
3 1 1 1.64685 31.44 46.49
2 2 2 1.57674 0.2 6.81
4 0 0 1.3655 12.69 74.25
3 3 1 1.25307 11.35 38.65
4 2 0 1.22134 0.54 8.67
4 2 2 1.11493 23.75 61.87
5 1 1 1.05116 6.88 34.2
3 3 3 1.05116 2.29 34.2
Go for highest symmetry
First pattern:

Apparent symmetry: 4-fold

Along which direction does the 4-fold axis lie in a cubic
system? <001>
<011>
<111>

aa

CaF2

c c
b
b
Along which direction does the 4-old axis lie in a cubic
system? <001>
<011>
<111>

aa

CaF2

c c
b
b
 probably this is <001>

(Cubic: [100], [010], [001] equivalent = <001>)

To do: measure the distances, compare to list d-hkl, index
consistently.
Step 1: Use the scalebar for the conversion
factor to 1/d-values.

Scalebar = R (in mm) L

R.d=L 34.4 mmÅ
42
equal to 1/0.08 nm 53.8 mmÅ
43
44 0.02 mmÅ
To do: measure the distances, compare to list d-hkl, index
consistently.
Step 1: Use the scalebar for the conversion
factor to 1/d-values.

Scalebar = R (in mm) L

R.d=L 34.4 mmÅ
42
equal to 1/0.08 nm 53.8 mmÅ
43
44 0.02 mmÅ
To do: measure the distances, compare to list d-hkl, index
consistently.
Step 1: Use the scalebar for the conversion
factor to 1/d-values.

Scalebar = R (in mm) L

R.d=L 34.4 mmÅ
42
equal to 1/0.08 nm 53.8 mmÅ
43
44 0.02 mmÅ
 Step 2: measure the distance of two reflections,
not on the same line, calculate the corresponding
d-value

1
2

Point 1 Point 2
d d
5.46 Å 5.46 Å
3.15 Å 3.15 Å
2.73 Å 2.73 Å
 Step 2: measure the distance of two reflections,
not on the same line, calculate the corresponding
d-value

1
2

Point 1 Point 2
d d
5.46 Å 5.46 Å
3.15 Å 3.15 Å
2.73 Å 2.73 Å
 Step 2: measure the distance of two reflections,
not on the same line, calculate the corresponding
d-value

1
2

Point 1 Point 2
d d
5.46 Å 5.46 Å
3.15 Å 3.15 Å
2.73 Å 2.73 Å
To do: measure the distances, compare to list d-hkl, index.
Step 3: look up in the table to which
reflection this corresponds

1
2

Point 1 Point 1 Point 2 Point 2

d hkl d hkl
5.46 Å 100 5.46 Å 100
3.15 Å 110 3.15 Å 110
2.73 Å 200 2.73 Å 200
To do: measure the distances, compare to list d-hkl, index.
Step 3: look up in the table to which
reflection this corresponds

1
2

Point 1 Point 1 Point 2 Point 2

d hkl d hkl
5.46 Å 100 5.46 Å 100
3.15 Å 110 3.15 Å 110
2.73 Å 200 2.73 Å 200
To do: measure the distances, compare to list d-hkl, index.
Step 3: look up in the table to which
reflection this corresponds

1
2

Point 1 Point 1 Point 2 Point 2

d hkl d hkl
5.46 Å 100 5.46 Å 100
3.15 Å 110 3.15 Å 110
2.73 Å 200 2.73 Å 200
Keep in mind: d-values valid for all equivalent {hkl}!

Step 4: make the indexation consistent

010
1
2

100

If point 1 is 200 then point 2 is 020 or 002.

Choose and stick with your choice.
 010
020 200

100
Step 5: calculate the zone-index

010
020 200

[100]
[010]
[001]
Step 5: calculate the zone-index

020 200

[100]
[010]
[001]
 Next zone

2
Which one would be easiest next? 3
4
 Next zone

2
Which one would be easiest next? 3
4
 Next zone: with reflections closest to the central beam.
5

Reflections closer to the central beam:

higher d-values

smaller amount of possible matches of hkl to this d

Measure the distance of two reflections, not on the
same line, calculate the corresponding d-value

1 2

Point 1 Point 2
d d
2.57 Å 2.57 Å
2.75 Å 2.73 Å
3.15 Å 3.15 Å
Measure the distance of two reflections, not on the
same line, calculate the corresponding d-value

1 2

Point 1 Point 2
d d
2.57 Å 2.57 Å
2.75 Å 2.73 Å
3.15 Å 3.15 Å
Measure the distance of two reflections, not on the
same line, calculate the corresponding d-value

1 2

Point 1 Point 2
d d
2.57 Å 2.57 Å
2.75 Å 2.73 Å
3.15 Å 3.15 Å
 Look up in the table to which reflection
this corresponds

1 2

hkl hkl
Point 1 110 Point 2 110
d = 3.15 Å 200 d = 2.73 Å 200
111 111
 Look up in the table to which reflection
this corresponds

1 2

hkl hkl
Point 1 110 Point 2 110
d = 3.15 Å 200 d = 2.73 Å 200
111 111
 Look up in the table to which reflection
this corresponds

1 2

hkl hkl
Point 1 110 Point 2 110
d = 3.15 Å 200 d = 2.73 Å 200
111 111
Make the indexation in a consistent manner.

1 2

Point 2 should be indexed as

200
020
-
200
all are correct
Make the indexation in a consistent manner.

1 2

Point 2 should be indexed as

200
020
-
200
all are correct
 Consistency:
This is a tilt series...

200 200

200 200

...so the common row needs to have the

same indices in all patterns
 Consistency:

1 200
3

Point 1 should be indexed as

111
-
111
--
111
all of the above are allowed
 Consistency:

1 200
3

Point 1 should be indexed as

111
-
111
--
111
all of the above are allowed
 Consistency:

111 200
-
111

-
If 111 for point 1

Point 3 is 111
311
-
311
 Consistency:

1 200

-
If 111 for point 1

Point 3 is 111
311
-
311
 Consistency:

111 200
-
111

-
If 111 for point 1
-
point 3 = 311
200
1

3
 Consistency:

111 200
-
111

-
If 111 for point 1
-
point 3 = 311
200
1
but
3 - ≠ dpoint3
d311
 Consistency:

111 200
-
111

-
If 111 for point 1
-
point 3 = 311
200
1
but
3 - ≠ dpoint3
d311
 Consistency:

111 200 200

- 1
111

3
= h1 k1 l1

1 and 3 have the same d-value

+
relation between 1 and 3 = vector 200
you need two indices such that
h3+2 = h1
k3+0 = k1
l3+0 = l1
- --
(also possible 111 and 111, make a choice and stick to it for the following patterns)
 Consistency:

111
022 200 200
022
-
111

Sum = 022.

Indeed consistent: if 𝑔 perpendicular to 𝑔200

then type of reflection needs to be 0kl.
 Calculate the zone-index

111
022 200
-
111

The zone-index is: [011]

-
[011]
 Calculate the zone-index

111
022 200
-
111

The zone-index is: [011]

-
[011]
 Consistency:
This is a tilt series...

...this helps to index the two remaining patterns!!!

The crystallite is threedimensional.

b
Zone axis : [0,0,0] So, the reciprocal lattice is threedimensional.
0,4,4

0,0,4
0,2,4
2,2,4
2,4,4 4,4,4

2,0,4
4,0,4
4,2,4

1,5,3
1,3,3
3,5,3
1,1,3
3,3,3
5,5,3
3,1,3
5,3,3
5,1,3
0,2,2
0,4,2
2,4,2

0,0,2 2,0,2
2,2,2
4,2,2
4,4,2

4,0,2
1,5,1
1,3,1
3,5,1
1,1,1
3,3,1
5,5,1
3,1,1
5,3,1
0,4,0
5,1,1

0,2,0 2,2,0
2,4,0
4,4,0

2,0,0 4,0,0
4,2,0
 ED patterns are sections of reciprocal space.
Zone axis : [0,0,0]

This section is the [001] zone.

0,0,4
0,4,4

0,2,4
2,2,4
2,4,4 4,4,4

2,0,4
4,0,4
4,2,4

1,5,3
1,3,3
3,5,3
1,1,3
3,3,3
5,5,3
3,1,3
5,3,3
5,1,3
0,2,2
0,4,2
2,4,2

0,0,2 2,0,2
2,2,2
4,2,2
4,4,2

4,0,2
1,5,1
1,3,1
3,5,1
1,1,1
3,3,1
5,5,1
3,1,1
5,3,1
0,4,0
5,1,1

0,2,0 2,2,0
2,4,0
4,4,0

2,0,0 4,0,0
4,2,0

[001]
 -
This section is the [011] zone:
Zone axis : [0,0,0]

0,4,4

0,0,4
0,2,4
2,2,4
2,4,4 4,4,4

2,0,4
4,0,4
4,2,4

1,5,3
1,3,3
3,5,3
1,1,3
3,3,3
5,5,3
3,1,3
5,3,3
5,1,3
0,2,2
0,4,2
2,4,2

0,0,2 2,0,2
2,2,2
4,2,2
4,4,2

4,0,2
1,5,1
1,3,1
3,5,1
1,1,1
3,3,1
5,5,1
3,1,1
5,3,1
0,4,0
5,1,1

0,2,0 2,2,0
2,4,0
4,4,0

2,0,0 4,0,0
4,2,0

-
[011]
 -
Zone axis : [0,0,0]
We tilt from [001] to [011]:
0,4,4

-
0,0,4
0,2,4
2,2,4
[011]
2,4,4 4,4,4

2,0,4
4,0,4
4,2,4

1,5,3
1,3,3
3,5,3
1,1,3
3,3,3
5,5,3
3,1,3
5,3,3
5,1,3
0,2,2
0,4,2
2,4,2

0,0,2 2,0,2
2,2,2
4,2,2
4,4,2

4,0,2
1,5,1
1,3,1
3,5,1
1,1,1
3,3,1
5,5,1
3,1,1
5,3,1
0,4,0
5,1,1

0,2,0 2,2,0
2,4,0
4,4,0

2,0,0 4,0,0
4,2,0

[001]
 So the tilt series gives pattern of consecutive sections
Zone axis : [0,0,0]
between these two end zones 0,4,4

-
0,0,4
0,2,4
2,2,4
[011]
2,4,4 4,4,4

2,0,4
4,0,4
4,2,4

1,5,3
1,3,3
3,5,3
1,1,3
3,3,3
5,5,3
3,1,3
5,3,3
5,1,3
0,2,2
0,4,2
2,4,2

0,0,2 2,0,2
2,2,2
4,2,2
4,4,2

4,0,2
1,5,1
1,3,1
3,5,1
1,1,1
3,3,1
5,5,1
3,1,1
5,3,1
0,4,0
5,1,1

0,2,0 2,2,0
2,4,0
4,4,0

2,0,0 4,0,0
4,2,0

[001]

Closest is 020.
Zone axis : [0,0,0]

0,4,4

-
0,0,4
0,2,4
2,2,4
[011]
2,4,4 4,4,4

2,0,4
4,0,4
4,2,4

1,5,3
1,3,3
3,5,3
1,1,3
3,3,3
5,5,3
3,1,3
5,3,3
5,1,3
0,2,2
0,4,2
2,4,2

0,0,2 2,0,2
2,2,2
4,2,2
4,4,2

051
4,0,2

1,3,1
x 1,5,1

3,5,1
1,1,1
3,3,1
5,5,1
3,1,1
5,3,1
0,4,0
5,1,1
-
0,2,0 2,2,0
[015]
2,4,0
4,4,0

2,0,0 4,0,0
4,2,0

[001]

Closest is 151.
Zone axis : [0,0,0]

0,4,4

0,0,4
0,2,4
2,2,4
[011]
2,4,4 4,4,4

2,0,4
4,0,4
4,2,4

1,5,3
1,3,3
3,5,3
1,1,3
3,3,3
5,5,3
3,1,3
5,3,3
5,1,3
0,2,2
0,4,2
2,4,2

0,0,2 2,0,2
2,2,2
4,2,2
4,4,2

4,0,2
031 1,5,1

x 1,3,1 -
1,1,1
3,3,1
3,5,1 [013]
5,5,1
3,1,1
5,3,1
0,4,0
5,1,1

0,2,0 2,2,0
2,4,0
4,4,0

2,0,0 4,0,0
4,2,0

[001]

Closest is 131.
Zone axis : [0,0,0]

0,4,4

0,0,4
0,2,4
2,2,4
[011]
2,4,4 4,4,4

2,0,4
4,0,4
4,2,4

1,5,3
1,3,3
3,5,3
1,1,3
3,3,3
5,5,3
3,1,3

042 5,1,3
5,3,3

0,2,2
0,4,2
2,4,2

0,0,2 -
2,0,2
2,2,2
4,2,2
4,4,2
[012]
4,0,2

021 1,3,1
1,5,1

1,1,1 x 3,5,1
3,3,1
5,5,1
3,1,1
5,3,1
0,4,0
5,1,1

0,2,0 2,2,0
2,4,0
4,4,0

2,0,0 4,0,0
4,2,0

[001]

Closest is 042.
Zone axis : [0,0,0]

0,4,4

0,0,4
0,2,4
2,2,4
[011]
2,4,4 4,4,4

2,0,4
4,0,4
4,2,4
053
1,3,3
x 1,5,3

3,5,3
1,1,3
3,3,3
5,5,3
3,1,3
5,3,3
5,1,3
0,2,2
0,4,2
2,4,2 -
[035]
0,0,2 2,0,2
2,2,2
4,2,2
4,4,2

4,0,2
1,5,1
1,3,1
3,5,1
1,1,1
3,3,1
5,5,1
3,1,1
5,3,1
0,4,0
5,1,1

0,2,0 2,2,0
2,4,0
4,4,0

2,0,0 4,0,0
4,2,0

[001]

Closest is 153.
Zone axis : [0,0,0]

0,4,4

-
0,0,4
0,2,4
2,2,4
[011]
2,4,4 4,4,4

2,0,4
4,0,4
4,2,4

1,5,3
1,3,3
3,5,3
1,1,3
3,3,3
5,5,3
3,1,3
5,3,3
5,1,3
0,2,2
0,4,2
2,4,2

0,0,2 2,0,2
2,2,2
4,2,2
4,4,2

4,0,2
1,5,1
1,3,1
3,5,1
1,1,1
3,3,1
5,5,1
3,1,1
5,3,1
0,4,0
5,1,1

0,2,0 2,2,0
2,4,0
4,4,0

2,0,0 4,0,0
4,2,0

[001]

Closest is 111. Perpendicular is 022.

 We can also see this in projection

0,4,4

0,0,4
0,2,4 2,2,4
2,4,4 4,4,4

2,0,4 4,0,4
4,2,4

1,5,3
1,3,3
1,1,3 3,5,3
3,3,3
3,1,3 5,5,3
5,3,3
5,1,3
0,2,2
0,4,2 2,4,2

0,0,2 2,0,2
2,2,2 4,2,2

4,4,2

4,0,2

1,5,1
1,3,1
1,1,1 3,5,1
3,3,1
3,1,1 5,5,1
5,3,1
5,1,1 0,4,0

0,2,0 2,2,0
2,4,0 4,4,0

2,0,0 4,0,0

4,2,0
 We can also see this in projection

4,0,4 2,2,4 0,4,4 4,4,4

0,0,4

2,0,4 0,2,4 4,2,4 2,4,4

5,1,3 1,3,3 3,3,3 5,3,3 1,5,3 3,5,3 5,5,3

1,1,3 3,1,3

2,0,2 0,2,2 4,2,2 2,4,2

0,0,2 4,0,2 2,2,2 0,4,2 4,4,2

3,1,1 5,1,1 1,3,1 3,3,1 5,3,1 1,5,1 3,5,1 5,5,1

1,1,1

4,0,0 2,2,0 0,4,0 4,4,0

2,0,0 0,2,0 4,2,0 2,4,0

Zone axis : [0,0,0]

We can also see this in projection

4,0,4 2,2,4 0,4,4 4,4,4

0,0,4

2,0,4 0,2,4 4,2,4 2,4,4

5,1,3 1,3,3 3,3,3 5,3,3 1,5,3 3,5,3 5,5,3

1,1,3 3,1,3

2,0,2 0,2,2 4,2,2 2,4,2

0,0,2 4,0,2 2,2,2 0,4,2 4,4,2

3,1,1 5,1,1 1,3,1 3,3,1 5,3,1 1,5,1 3,5,1 5,5,1

1,1,1

4,0,0 2,2,0 0,4,0 4,4,0

2,0,0 0,2,0 4,2,0 2,4,0

xis : [0,0,0]

We can also see this in projection

which is easier to draw manually...
4,0,4 2,2,4 4,4,4
0,4,4
0,0,4

2,0,4 4,2,4
0,2,4 2,4,4

5,1,3 5,3,3
3,3,3
1,3,3 5,5,3
3,5,3
1,5,3
3,1,3
1,1,3

2,0,2 4,2,2
0,2,2 2,4,2

4,0,2
0,0,2 2,2,2 4,4,2
0,4,2

5,1,1
3,1,1 5,3,1
3,3,1
1,3,1 5,5,1
3,5,1
1,5,1
1,1,1

4,0,0 2,2,0 4,4,0

0,4,0

2,0,0 4,2,0
0,2,0 2,4,0
xis : [0,0,0]

4,0,4 2,2,4 4,4,4

0,4,4
0,0,4

2,0,4 4,2,4
0,2,4 2,4,4

5,1,3 5,3,3
3,3,3
1,3,3 5,5,3
3,5,3
1,5,3
3,1,3
1,1,3

2,0,2 4,2,2
0,2,2 2,4,2

4,0,2
0,0,2 2,2,2 4,4,2
0,4,2

5,1,1
3,1,1 5,3,1
3,3,1
1,3,1 5,5,1
3,5,1
1,5,1
1,1,1

4,0,0 2,2,0 4,4,0

0,4,0

2,0,0 4,2,0
0,2,0 2,4,0

[001]
xis : [0,0,0]

4,0,4 2,2,4 4,4,4

0,4,4
0,0,4

2,0,4 4,2,4
0,2,4 2,4,4

5,1,3 5,3,3
3,3,3
1,3,3 5,5,3
3,5,3
1,5,3
3,1,3
1,1,3

2,0,2 4,2,2
0,2,2 2,4,2

4,0,2
0,0,2 2,2,2 4,4,2
0,4,2

-
5,1,1
3,1,1
1,1,1 5,3,1
3,3,1
1,3,1 5,5,1
3,5,1
1,5,1
[015]

4,0,0 2,2,0 4,4,0

0,4,0

2,0,0 4,2,0
0,2,0 2,4,0

[001]
xis : [0,0,0]

4,0,4 2,2,4 4,4,4

0,4,4
0,0,4

2,0,4 4,2,4
0,2,4 2,4,4

5,1,3 5,3,3
3,3,3
1,3,3 5,5,3
3,5,3
1,5,3
3,1,3
1,1,3

2,0,2 4,2,2
0,2,2 2,4,2

2,2,2 4,4,2
0,4,2
-
4,0,2
0,0,2
[013]

-
5,1,1
3,1,1
1,1,1 5,3,1
3,3,1
1,3,1 5,5,1
3,5,1
1,5,1
[015]

4,0,0 2,2,0 4,4,0

0,4,0

2,0,0 4,2,0
0,2,0 2,4,0

[001]
xis : [0,0,0]

4,0,4 2,2,4 4,4,4

0,4,4
0,0,4

2,0,4 4,2,4
0,2,4 2,4,4

5,1,3
3,1,3
1,1,3 5,3,3
3,3,3
1,3,3 5,5,3
3,5,3
1,5,3 -
[012]

2,0,2 4,2,2
0,2,2 2,4,2

2,2,2 4,4,2
0,4,2
-
4,0,2
0,0,2
[013]

-
5,1,1
3,1,1
1,1,1 5,3,1
3,3,1
1,3,1 5,5,1
3,5,1
1,5,1
[015]

4,0,0 2,2,0 4,4,0

0,4,0

2,0,0 4,2,0
0,2,0 2,4,0

[001]
xis : [0,0,0]

4,0,4 2,2,4 4,4,4

0,4,4
0,0,4

2,0,4 4,2,4
0,2,4 2,4,4

-
[035]
5,1,3
3,1,3
1,1,3 5,3,3
3,3,3
1,3,3 5,5,3
3,5,3
1,5,3 -
[012]

2,0,2 4,2,2
0,2,2 2,4,2

2,2,2 4,4,2
0,4,2
-
4,0,2
0,0,2
[013]

-
5,1,1
3,1,1
1,1,1 5,3,1
3,3,1
1,3,1 5,5,1
3,5,1
1,5,1
[015]

4,0,0 2,2,0 4,4,0

0,4,0

2,0,0 4,2,0
0,2,0 2,4,0

[001]
xis : [0,0,0]

-
[011]

4,0,4 2,2,4 4,4,4

0,4,4
0,0,4

2,0,4 4,2,4
0,2,4 2,4,4

-
[035]
5,1,3
3,1,3
1,1,3 5,3,3
3,3,3
1,3,3 5,5,3
3,5,3
1,5,3 -
[012]

2,0,2 4,2,2
0,2,2 2,4,2

2,2,2 4,4,2
0,4,2
-
4,0,2
0,0,2
[013]

-
5,1,1
3,1,1
1,1,1 5,3,1
3,3,1
1,3,1 5,5,1
3,5,1
1,5,1
[015]

4,0,0 2,2,0 4,4,0

0,4,0

2,0,0 4,2,0
0,2,0 2,4,0

[001]
 Right upper zone:

Measure the distance of two reflections, not on the

same line, calculate the corresponding d-value

2
200

Point 2
d
We already know the 1.22 Å
first point: 200. 1.11 Å
1.05 Å
 Right upper zone:

Measure the distance of two reflections, not on the

same line, calculate the corresponding d-value

2
200

Point 2
d
We already know the 1.22 Å
first point: 200. 1.11 Å
1.05 Å
Look up in the table to which reflection this corresponds:
We know already it is either 151 or 131 or 042 or 153

2
200

Point 2 Point 2
d hkl
1.05 Å 151
131
042
Look up in the table to which reflection this corresponds:
We know already it is either 151 or 131 or 042 or 153

2
200

Point 2 Point 2
d hkl
1.05 Å 151
131
042
 If this were not a tilt series...

Point 2 could have been at first sight

both 115 and 333...

In this case:
Can compare the experimental angles between reflections
to the theoretical angles

-either formulas from any standard crystallography work

-or simply simulate the different zones calculated for the

different options (JEMS, CrystalKit, Carine,...) to check this

Or in this particular case of 333: you would need to see 111 and 222 at 1/3 and 2/3 of the distance.
 Calculate the zone-index

151
200

The zone-index is:

[0 2 10]
[0 1 5]
-
[0 1 5]
 Calculate the zone-index

151
200

The zone-index is:

[0 2 10]
[0 1 5]
-
[0 1 5]
What if you didn’t know the material?
-
[011]
You would just need to check
more possibilities: -
[034]
-
[023]
-
[035]
-
[012]
043 053 -
[025]
-
[013]
032 052 -
[014]
-
[015]
011 021 031 041 051

010 [001]
When indexed correctly, the patterns in between
have to give you one of these as zone-index.
 Pattern bottom left:

Measure the distance of two reflections, not on the

same line, calculate the corresponding d-value

2
200

Point 2
d
1.65 Å
1.58 Å
1.37 Å
 Pattern bottom left:

Measure the distance of two reflections, not on the

same line, calculate the corresponding d-value

2
200

Point 2
d
1.65 Å
1.58 Å
1.37 Å
Look up in the table to which reflection this corresponds.
We know already it is either: 151 or 131 or 042 or 153

2
200

Point 2 Point 2
d hkl
1.65 Å 042
131
153
Look up in the table to which reflection this corresponds.
We know already it is either: 151 or 131 or 042 or 153

2
200

Point 2 Point 2
d hkl
1.65 Å 042
131
153
The indexation is indeed consistent.

062131
- 200
131
 -
[013]
062131
- 200
131
Make your analysis easier by not taking
ED patterns from separate crystals, but
taking different ED patterns from the
same crystallite, if possible.

=“Tilt series”
So now you have indexed these four patterns.

[001] -
[015]
151
020 200 200

- -
[013] [011]
131
200 111 200
...indexed patterns give you info on fase,
orientation, cell parameters,...

[001] -
[015]
151
020 200 200

- -
[013] [011]
131
200 111 200
 What if you do not have any prior
knowledge when you have to
index?

Analyse the patterns  try to propose basis vectors

(For example reflections closest to the central beam)

Same system as previous slides:

can you index all reflections?

If not, adapt your choice of

basis vectors and try again.
If we do not know the space group, the next step would
be to determine it!
(maybe you started from 0 or you had only cell parameters from XRD or...)

[001] -
[015]
151
020 200 200

- -
[013] [011]
131
200 111 200
 Space group?

Reflection conditions + Point Group (CBED)

(SAED)

P no reflection conditions
F h+k=2n, k+l=2n, h+l=2n
I h+k+l=2n
A/B/C k+l=2n/h+k=2n/h+k=2n
SAED
glide planes conditions on hk0/h0l/0kl
screw axes conditions on h00/0k0/00l
mirror planes, inversion no extra conditions
centre, rotation axes CBED
Reflection conditions can be looked up in tables in
International Tables for Crystallography Vol. A

Or using freeware such as Space Group Explorer

Be careful: forbidden reflections can occur because of
dynamical diffraction

Incident electron wave

 For example possible

When reflection
conditions say this:
Can see this:

020 010

100 100
 F(110) ≠0

020
F(010)=0

100
F(100)≠0

Need to tilt to remove these paths...

 Destroy double diffraction paths by tilting.

If becomes

then extinct, was due to DD

If stays

then not extinct.

You will need this table (from IT volume A)

Figure out reflection

conditions for these
sets.
Step 1: determine the reflection conditions from the patterns.
h+k+l=2n
hkl: h+k, k+l, h+l=2n
h+k=2n
[001] -
[015]
151
020 200 200

- -
[013] [011]
131
200 111 200
Step 1: determine the reflection conditions from the patterns.
h+k+l=2n
hkl: For these patterns
h+k, k+l, h+l=2n both would be
h+k=2n good....!?
[001] -
[015]
151
020 200 200

- -
[013] [011]
131
200 111 200
This means we do not have sufficient information.

By coincidence
-
we missed [012], which will make the difference.

042
200
xis : [0,0,0]

-
[011]

4,0,4 2,2,4 4,4,4

0,4,4
0,0,4

2,0,4 4,2,4
0,2,4 2,4,4

-
[035]
5,1,3
3,1,3
1,1,3 5,3,3
3,3,3
1,3,3 5,5,3
3,5,3
1,5,3 -
[012]

2,0,2 4,2,2
0,2,2 2,4,2

2,2,2 4,4,2
0,4,2
-
4,0,2
0,0,2
[013]

-
5,1,1
3,1,1
1,1,1 5,3,1
3,3,1
1,3,1 5,5,1
3,5,1
1,5,1
[015]

4,0,0 2,2,0 4,4,0

0,4,0

2,0,0 4,2,0
0,2,0 2,4,0

[001]
This means we do not have sufficient information.

By coincidence
-
we missed [012], which will make the difference.

042 hkl:
200 h+k+l=2n
h+k, k+l, h+l=2n
h+k=2n
This means we do not have sufficient information.

By coincidence
-
we miss [012], which will make the difference.

042 hkl:
200 h+k+l=2n
h+k, k+l, h+l=2n
h+k=2n

For only h+k=2n there is no reason why

021 would be absent.
It is possible to draw the wrong
conclusions if you do not have
enough zones!
Step 1: determine the reflection conditions from the patterns.
k=2n
0kl: k,l=2n
k+l=2n
[001] -
[015]
151
020 200 200

- -
[013] [011] 042
131
200 111 200
200
Step 1: determine the reflection conditions from the patterns.
k=2n
0kl: k,l=2n
k+l=2n
[001] -
[015]
151
020 200 200

- -
[013] [011] 042
131
200 111 200
200
Step 1: determine the reflection conditions from the patterns.
h=2n
hhl: h,l=2n
h+l=2n
[001] -
[015]
151
020 200 200

- -
[013] [011] 042
131
200 111 200
200
Step 1: determine the reflection conditions from the patterns.
h=2n
hhl: h,l=2n
h+l=2n
[001] -
[015]
151
020 200 200

- -
[013] [011] 042
131
200 111 200
200
Step 1: determine the reflection conditions from the patterns.
no condition
00l: l=2n
l=4n
[001] -
[015]
151
020 200 200

- -
[013] [011] 042
131
200 111 200
200
Step 1: determine the reflection conditions from the patterns.
no condition
00l: l=2n
l=4n
[001] -
[015]
151
020 200 200

- -
[013] [011] 042
131
200 111 200
200
Step 2: look up the matching extinction
symbol in the International Tables of
Crystallography.

?
?
200 and 020 could be due to double
diffraction...

[001] -
[015]
151
020 200 200

- -
[013] [011]
131
200 111 200
200 and 020 could be due to double
diffraction...
 Tilt around 200 until all other
reflections gone except h00 axis:
[001] -
[015]
151
020 200 200

- -
[013] [011]
131
200 111 200
 200 and 020 could be due to double
diffraction...
Tilt around 200 until all other reflections
gone except h00 axis:

200 does not disappear

 It is not double diffraction
 00l: l=2n
not 00l: l=4n
Step 2: look up the matching extinction symbol in
the International Tables of Crystallography.
From the reflection conditions you get
the extinction symbol:

F---
From the reflection conditions you get
the extinction symbol:

F---

This still leaves 5 possible space groups

- - -
F23 Fm3 F432 F43m Fm3m
 From the reflection conditions you get
the extinction symbol:

F---

This still leaves 5 possible space groups

- -
F23 Fm3 F432 F43m Fm3m

Only difference: rotation axes and mirror planes

cannot be derived from reflection conditions

 need CBED
Convergent Beam Electron Diffraction

CBED
 Diffraction groups vs. Point groups
6mm1R
3m1R
6mm
6mRmR
61R
31R
6
6RmmR
3m
3mR
6R
3
4mm1R
4RmmR
4mm
4mRmR
41R
4R
4
2mm1R
2RmmR
2mm
2mRmR
m1R
m
mR
21R
Table redrawn
2R
from B.F. Buxton,
2
J.A. Eades, J.W.
1R
Steeds, G.M.
1
Rackham: Phil.
4/mmm

6/mmm
Trans. R. Soc.
mmm

-42m

-43m
-6m2
4mm

6mm

m3m
mm2
2/m

4/m

6/m
-3m
222

422

622

432
3m

m3
London, 281
32

23
-1

-4

-3

-6
m
1
2

(1976) 171
 Diffraction groups vs. Point groups
6mm1R
3m1R
6mm
6mRmR
61R
31R
6
6RmmR
3m
3mR
6R
3
4mm1R
4RmmR
4mm
4mRmR
41R
4R
4
2mm1R
2RmmR
2mm
2mRmR
m1R
m
mR
21R
Table redrawn
2R
from B.F. Buxton,
2
J.A. Eades, J.W.
1R
Steeds, G.M.
1
Rackham: Phil.
4/mmm

6/mmm
Trans. R. Soc.
mmm

-42m

-43m
-6m2
4mm

6mm

m3m
mm2
2/m

4/m

6/m
-3m
222

422

622

432
3m

m3
London, 281
32

23
-1

-4

-3

-6
m
1
2

(1976) 171
For CBED you need sufficiently thick crystals:

10 nm 20 nm 30 nm

40 nm 50 nm
Table from: J.A. Eades,
Convergent beam diffraction, in:
Electron Diffraction Techniques,
volume 1, ed. J. Cowley, Oxford
University Press, 1992
Whole pattern projection symmetry

Symmetry is 4mm.
Table from: J.A. Eades,
Convergent beam diffraction, in:
Electron Diffraction Techniques,
volume 1, ed. J. Cowley, Oxford
University Press, 1992
Table from: J.A. Eades,
Convergent beam diffraction, in:
Electron Diffraction Techniques,
volume 1, ed. J. Cowley, Oxford
University Press, 1992
 Diffraction groups vs. Point groups
6mm1R
3m1R
6mm
6mRmR
61R
31R
6
6RmmR
3m
3mR
6R
3
4mm1R
4RmmR
4mm
4mRmR
41R
4R
4
2mm1R
2RmmR
2mm
2mRmR
m1R
m
mR
21R
Table redrawn
2R
from B.F. Buxton,
2
J.A. Eades, J.W.
1R
Steeds, G.M.
1
Rackham: Phil.
4/mmm

6/mmm
Trans. R. Soc.
mmm

-42m

-43m
-6m2
4mm

6mm

m3m
mm2
2/m

4/m

6/m
-3m
222

422

622

432
3m

m3
London, 281
32

23
-1

-4

-3

-6
m
1
2

(1976) 171
[111]
[111]

6mm
Table from: J.A. Eades,
Convergent beam diffraction, in:
Electron Diffraction Techniques,
volume 1, ed. J. Cowley, Oxford
University Press, 1992
 Diffraction groups vs. Point groups
6mm1R
3m1R
6mm
6mRmR
61R
31R
6
6RmmR
3m
3mR
6R
3
4mm1R
4RmmR
4mm
4mRmR
41R
4R
4
2mm1R
2RmmR
2mm
2mRmR
m1R
m
mR
21R
Table redrawn
2R
from B.F. Buxton,
2
J.A. Eades, J.W.
1R
Steeds, G.M.
1
Rackham: Phil.
4/mmm

6/mmm
Trans. R. Soc.
mmm

-42m

-43m
-6m2
4mm

6mm

m3m
mm2
2/m

4/m

6/m
-3m
222

422

622

432
3m

m3
London, 281
32

23
-1

-4

-3

-6
m
1
2

(1976) 171
 Diffraction groups vs. Point groups
6mm1R
3m1R
6mm
6mRmR
61R
31R
6
6RmmR
3m
3mR
6R
3
4mm1R
4RmmR
4mm
4mRmR
41R
4R
4
2mm1R
2RmmR
2mm
2mRmR
m1R
m
mR
21R
Table redrawn
2R
from B.F. Buxton,
2
J.A. Eades, J.W.
1R
Steeds, G.M.
1
Rackham: Phil.
4/mmm

6/mmm
Trans. R. Soc.
mmm

-42m

-43m
-6m2
4mm

6mm

m3m
mm2
2/m

4/m

6/m
-3m
222

422

622

432
3m

m3
London, 281
32

23
-1

-4

-3

-6
m
1
2

(1976) 171
 Diffraction groups vs. Point groups
6mm1R
3m1R
6mm
6mRmR
61R
31R
6
6RmmR
3m
3mR
6R
3
4mm1R
4RmmR
4mm
4mRmR
41R
4R
4
2mm1R
2RmmR
2mm
2mRmR
m1R
m
mR
21R
Table redrawn
2R
from B.F. Buxton,
2
J.A. Eades, J.W.
1R
Steeds, G.M.
1
Rackham: Phil.
4/mmm

6/mmm
Trans. R. Soc.
mmm

-42m

-43m
-6m2
4mm

6mm

m3m
mm2
2/m

4/m

6/m
-3m
222

422

622

432
3m

m3
London, 281
32

23
-1

-4

-3

-6
m
1
2

(1976) 171
 CBED

SAED
 So, sometimes just whole pattern projection
symmetry is enough if you combine it with the
reflection conditions from SAED.
Try it yourself on example SnO2
SAED CBED

Example: rutile-type SnO2

Projection whole pattern symmetry [001]

4
4mm
2mm
Projection whole pattern symmetry [001]

4
4mm
2mm
 Projection WP: 4mm

Projection diffraction group:

Table Eades

4
4RmmR
4mm1R

Table from: J.A. Eades,

Convergent beam diffraction, in:
Electron Diffraction Techniques,
volume 1, ed. J. Cowley, Oxford
University Press, 1992
 Projection WP: 4mm

Projection diffraction group:

Table Eades

4
4RmmR
4mm1R

Table from: J.A. Eades,

Convergent beam diffraction, in:
Electron Diffraction Techniques,
volume 1, ed. J. Cowley, Oxford
University Press, 1992
 Projection diffraction group:
4mm1R

Possible diffraction groups:

4mRmR
4mm
4RmmR
4mm1R

Table from: J.A. Eades,

Convergent beam diffraction, in:
Electron Diffraction Techniques,
volume 1, ed. J. Cowley, Oxford
University Press, 1992
 6mm1R
3m1R
6mm
6mRmR
61R
31R
6
6RmmR
3m
3mR
6R
3
4mm1R
4RmmR
4mm
4mRmR
41R
4R
4
2mm1R
2RmmR
2mm
2mRmR
m1R
m
mR
Table redrawn 21R
from B.F. Buxton, 2R
J.A. Eades, J.W. 2
Steeds, G.M.
1R
Rackham: Phil.
1
Trans. R. Soc.
4/mmm

6/mmm
London, 281
mmm

-42m

-43m
-6m2
4mm

6mm

m3m
mm2
2/m

4/m

6/m
-3m
222

422

622

432
(1976) 171
3m

m3
32

23
-1

-4

-3

-6
m
1
2

6
 [...] [...]

What will be useful to narrow it down further?

look at the bright field symmetry
look at the whole pattern symmetry
 [...] [...]

What will be useful to narrow it down further?

look at the bright field symmetry
look at the whole pattern symmetry
Whole
Pattern
projection
symmetry

Whole
pattern
symmetry
WP symmetry

4
4mm
2mm
WP symmetry

4
4mm
2mm
[...] [...]
6mm1R
3m1R
6mm
6mRmR
61R
31R
6
6RmmR
3m
3mR
6R
3
4mm1R
4RmmR
4mm
4mRmR
41R
4R
4
2mm1R
2RmmR
2mm
2mRmR
m1R
m
mR
21R
2R
2
1R
1
4/mmm

6/mmm
mmm

-42m

-43m
-6m2
4mm

6mm

m3m
mm2
2/m

4/m

6/m
-3m
222

422

622

432
3m

m3
32

23
-1

-4

-3

-6
m
1
2

6
Projection whole pattern [101]

(smaller cond.ap.)
2
m
2mm
Projection whole pattern [101]

(smaller cond.ap.)
2
m
2mm
 Projection
whole pattern:
2mm

Possible projection
diffraction group:
21R
m1R
2mm1R
 Projection
whole pattern:
2mm

Possible projection
diffraction group:
21R
m1R
2mm1R
 Projection
whole pattern:
2mm

Possible projection
diffraction group:
21R
m1R
2mm1R
Whole pattern [101]

(smaller cond.ap.)
2
m
2mm
Whole pattern [101]

(smaller cond.ap.)
2
m
2mm
 Whole pattern
m

Diffraction group:

2mm
2RmmR
2mm1R
 Whole pattern
m

Diffraction group:

2mm
2RmmR
2mm1R
6mm1R
3m1R
6mm
6mRmR
61R
31R
6
6RmmR
3m
3mR
6R
3
4mm1R
4RmmR
4mm
4mRmR
41R
4R
4
2mm1R
2RmmR
2mm
2mRmR
m1R
m
mR
21R
2R
2
1R
1
4/mmm

6/mmm
mmm

-42m

-43m
-6m2
4mm

6mm

m3m
mm2
2/m

4/m

6/m
-3m
222

422

622

432
3m

m3
32

23
-1

-4

-3

-6
m
1
2

6
Possible point groups

4/mmm

m3m
 What would make a difference further?

For example:
-cell parameters

-look for a third zone etc.

-SAED for reflection conditions

 For example, if you need

cell parameters a=b= 4.72 Å, c=3.16 Å

to be able to index all patterns,

the point group is

4/mmm

m3m
 For example, if you need

cell parameters a=b= 4.72 Å, c=3.16 Å

to be able to index all patterns,

the point group is

4/mmm

m3m
Then you would combine this again with reflection
conditions (not derived in this exercise) to get the
space group.
CBED

SAED

Space Group P42/mnm

At the end of this lecture you should be able to

(1) index SAED patterns in case the cell parameters

are already known
(2) determine the possible space groups from SAED
patterns

(3) determine possible point groups from CBED

patterns

Combine (2) and (3) to find the space group.

Working page for indexing