Chapter 3

Basic Crystallography and Electron Diffraction from Crystals

Lecture 13

CHEM 793, 2008 Fall

Announcement
Midterm Exam: Oct. 22, Wednesday, 2:30 4:30

CHEM 793, 2008 Fall

Indexing Diffraction Pattern

000
000

000

FCC single crystal Pattern

FCC Polycrystalline ring Pattern

CHEM 793, 2008 Fall

Indexing Diffraction Pattern

Indexing means labeling the diffraction rings and spot with appropriate
(hkl)
Key to determining:
interplanar spacing: d-spacing
lattice parameter, a
crystal orientation
nature of defects
Cannot do phase identification or defect analysis until diffraction pattern
is indexed.

Dont take any TEM image of a crystal without a

corresponding diffraction pattern!
CHEM 793, 2008 Fall

Indexing diffraction pattern is just application of the reciprocal lattice and

kinematical theory of electron diffraction

1. Laue Condition
Diffraction occurs when the vector of diffraction wave K is a vector the reciprocal
lattice, ghkl), i.e. K=ghkl. This condition is equivalent to Bragg Law.
Braggs Law actually is mathematically correct but physically wrong, since it
doesnt consider 3-D of a crystal
Laue condition describes the crystal diffraction in a rigorous fashion
K, KI and KD may be described in terms
of vector triangle as shown below

Indexing DP is just to look for a reciprocal lattice

of a zone axis [vuw] satisfying Laue condition

KI

CHEM 793, 2008 Fall

KD

2. Zone axis at intersection of plane (h1k1l1) and (h2k2l2)

r* r*
r*
v
g hkl = ha + kb + lc

hu + kv + lw = 0

If (h1k1l1) and (h2k2l2) belong to zone [uvw], then we can find the zone axis [uvw],
i.e. the direction of intersection of two planes (h1k1l1) and (h2k2l2)
Using zone law to look for the reciprocal
lattice of a zone axis [uvw]
[uvw]

(h3k3l3)

(h2k2l2)

u
h1u + k1v + l1w = 0
or h1

h
u
k
v
l
w
+
+
=
0
2
2
2
h2

u:v: w=

k1

l1

k2

l2

: (1)

v w
k1 l1
k2

l2

h1

l1 h1
:
l2 h2

h2

u = k1l2 k2l1; v = h2l1 h1l2; w = h1k2 h2k1

h2k2l2

h3k3l3

(h1k1l1)

h1k1l1

000

A section
reciprocal
CHEM of
793,
2008 Fall lattice on (uvw)

=0
k1
k2

3. The addition rule

You only need find two
reciprocal lattice then you
can construct whole pattern

r
v
v
g h1k1l 1 + g h2 k 2l 2 = g ( h1 + h2 )( k1 + k2 )(l1 +l2 )
e.g .
v
v
v
g101 + g 001 = g102
CHEM 793, 2008 Fall

4. Angle between plane normals (h1k1l1) and (h2k2l2)

r*
r*
r*
v
g h1k1l1 = h1a + k1b + l1c
r*
r*
r*
v
g h2 k2l 2 = h2 a + k 2b + l2 c
v
v
g h1k1l1 g h2 k2l 2
cos = v
v
g h1k1l1 g h2 k2l 2

Inspecting the angle is easy to identify the crystal structure based on

the DP database

CHEM 793, 2008 Fall

5. Structure factor rule

1. bcc structure factor rule: The sum of the three integers h, k, l must be an even
number.
For example, bcc W, the lowest-order allowed diffractions are (110), (200), (211),
(220), (310), (222), (321), (440), (330), (411), (420), etc., but diffractions such as
(100), (111), (210), etc. are forbidden.
2. For fcc factor rule: the three integers h,k,l must be all even or all odd. For
example, the lowest order diffractions are (111), (200), (220), (311), (222), (400),
(331), (420), but other diffractions such as the (100), (110), (210), (211), etc. are
forbidden.
3. For sc crystal, any crystal (hkl) produces the strong diffraction

Using the structure factor rule to exclude the forbidden vectors from the candidate
reciprocal lattices

CHEM 793, 2008 Fall

Indexing Diffraction Patterns

Three typical DPs:

CHEM 793, 2008 Fall

A single perfect
crystal

A small number of
grains- note that
even with three
grains the spots
begin to form circle

A large number pf
randomly oriented
grains-the spots
have now merged
into rings.

The amophorous
materials is also
forming the ring
pattern (usually
only one ring)

Index equation derivation

Bragg Law

2 d hkl sin = n
2 d hkl sin =

Diffracted beam

Incident beam

2
hkl
r: spot
distance

Q is samll
2 d

CHEM 793, 2008 Fall

000

L: camera length

2 =

r
L

r
=
L
d
or
rd

= L , L is called
a
d =
h2 + k 2 + l2
L
L
h2 + k
r =
=
d
a

and

Diffracted beam

Incident beam

camera

+ l

L: camera length

2
hkl
r: spot
distance

000

CHEM 793, 2008 Fall

constant

L L
r=
=
d
a
r1
=
r2

h1 + k1 + l1

h2 + k 2 + l2
2

h2 + k 2 + l 2

d2
=
d1

The angle ( ) between r 1 and r 2

cos =

Diffracted beam

Incident beam

h1 h2 + k1 k 2 + l1l 2
h12 + k12 + l12 h22 + k 22 + l 22

L: camera length

2
hkl
r: spot
distance

000

CHEM 793, 2008 Fall

Example: 1. Analysis of polycrystalline diffraction pattern--- ring pattern

(although amorphous materials also produce ring pattern, we only discuss
the crystalline materials)
(a)

(b)

(c)

(d)

In (a) and (c), the grain size is larger than in (b) and
(d) respectively. So the rings in (a) and (c) are
made up of discrete spots. A finer grain size, as in
(b) and (d), produces more continuous ring
patterns, but width of the rings associated with the
diffraction intensity become broader and can be
CHEM 793, 2008 Fall
used
as an inverse measure of the grain size.

1. Analysis of polycrystalline diffraction pattern--- ring pattern

Incident beam

Small grains

Diffracted beams
from (hkl) planes in
each particles

(hkl) ring

Mechanism of forming ring

pattern

The geometry of formation of a single

(hkl) ring by accumulation of (hkl)
beams from different grains.

CHEM 793, 2008 Fall

Mechanism of forming ring

pattern

The geometry of formation of a single (hkl) ring by accumulation of (hkl) beams from different
grains.
If the grains in a polycrystalline material are randomly oriented or weakly textured, then the
reciprocal vector g to each diffracting plane will be oriented in all possible direction.
Since the length of a particular g is a constant, these vectors g will describe a sphere with
radius of |g|.
The intersection of such a sphere with Ewald sphere is a circle, and therefore the diffraction
pattern will consist of concentric rings.
If grains are sufficiently large, individual reflections can be seen in the rings as in Fig. a
For fine grains the diffraction patternCHEM
would793,
look
more
2008
Falllike that shown in Fig. b.

Planar Ewald sphere

a
Planar Ewald sphere

If texture is present, then one or more rings

may be absent, or the intensity in any
particular ring may vary along the ring. From
an analysis of these intensity distributions,
one can, in principal, derive information
about the thin foil texture.
Fig. a shows a texture ring pattern with
more intense over a certain angular range,
and the corresponding interception of the
Ewald sphere with reciprocal lattice
Fig. b shows a DF image of textured grains,
taken from a brighter portion of one of the hkl
rings, showing an equiaxed structure.

Fig.c shows the elongated spots or acrs in

diffraction pattern, since the specimen is
textured about a direction at an angle to the
CHEM 793, 2008 Fall
beam.

1. Analysis of polycrystalline diffraction pattern--- ring pattern

(b)
r1

r2
r3

A polycrystalline ring pattern is essentially similar to an Xray Debye-Scherrer pattern. It can provide information
about the crystal structure and lattice spacings of the
sample, although the latter information is not as
accurate as from X-rays. If the camera constant is
known, the procedure is as follows:
1. Measuring the radii of the rings r1, r2, r3, etc.
2. Calculating the d-spacings d1, d2, d3, etc. of the
planes giving rise to these rings using equation:
rd=L.
3. Having obtained the d-spacings of the rings, then an
unknown material can often be identified with the help
of a reference source such as ASTM handbook or
ICDD PDF card, which lists the d-spacings of the
thousands of materials.
4. Indexing the ring pattern, the structure factor must be
considered.
5. One of the common uses of a polycrystalline ring
pattern
is for
calibrating
the microscope and obtaining
CHEM
793,
2008
Fall
the camera constant.

Example: index a ring pattern and determine if the pattern is fcc or bcc pattern
1. Measure the diameter of rings, and calculate the ratios of these diameters (rn/r1)

Ring diameter (mm) (2rn) Ratios of diameter (rn/r1)

(b)

2r1
r1

2r2

r2

2r3

r3

2r4

r4

2. Try fcc first using allowed low order diffraction planes (hkl)
considering structure factor,. Check if the ratios of h2+k2+l2 match the
ratios of diameters (rn/r1), and thereby determine the diffraction planes
and type of cubic.

L L
r=
=
h2 + k 2 + l 2
d
a
2

Allowed hkl

M=h2+k2+l2

h1 + k1 + l1
r1
d
=
= 2
2
2
2
r2
d1
h2 + k 2 + l2
CHEM 793, 2008 Fall

Ratios Mn/M1

Example: index a ring pattern and determine if the pattern is fcc or bcc pattern

Ring diameter (mm) (2rn)

(311)
(220)
r1

(200)

r2

(111)

r3
r4

2r1

16.5

2r2

19.1

1.157575758

2r3

26.9

1.63030303

2r4

31.5

1.909090909

fcc Allowed
hkl

r=

L L
=
h2 + k 2 + l 2
d
a
2

h1 + k1 + l1
r1
d
=
= 2
2
2
2
r2
d1
h2 + k 2 + l2

Ratios of diameter (rn/r1)

M=h^2+k^2+l^2

Ratios of M (Mn/M1)

111

1.732050808

200

1.154700538

220

2.828427125

1.632993162

311

3.31662479

1.914854216

So ratios (rn/r1) match Mn/M1. This ring pattern is fcc

pattern. Indexing is (111), (200), (220) and (311)
from
inside
outside
CHEM
793,to
2008
Fall

2. Ratio technique to index the diffraction pattern (analysis of single crystal pattern)
Any 2-D section of a reciprocal lattice can be defined by two vectors so we only need to index 2
spots. All others can be deduced by vector addition.
If the crystal structure is known, the ratio procedure for indexing is:
1.Choose one spot to be the origin. Note: it does not matter which spot you choose.
2.Measure the spacing of one prominent spot, r1. Note: for greater accuracy measure across
several spots in a line and average their spacings.
3.Measure the spacing of a second spot, r2. Note: the second spot must not be collinear with
the first spot and the origin. And the best way is choose r2 perpendicular to r1 if possible.
4.Measure the angle between the spots, .
5.Prepare a table giving the ratios of the spacings of permitted diffraction planes in the known
structure. Hint: start with the widest spaced plane (smallest r). You only ever need to do this once
for each structure.
6.Take the measured ratio r1/r2 and locate a value close to this in the table.
7.Assign the more widely-spaced plane (usually with lower indices) to the shorter r value.
8.Calculate the angle between pair of planes of the type you have indexed. If the experimental
angel , agrees with one of the possible values - accept the indexing. If not, revisit the table and select
another possible pair of planes.
10.Finish indexing the pattern by vector addition.

Any 2-D section of a reciprocal lattice can be defined by two vectors

so we
only need
to index
CHEM
793, 2008
Fall2 spots. All others can be deduced by
vector addition.

Example: A fcc structure diffraction patterns are shown below

The ratio of interplanar spacings between two
different planes, d1 and d2 is

r1
=
r2

h1 + k1 + l1
2

h2 + k 2 + l 2

d2
d1

Index procedure:
Angle: 90
0.65 cm
1.10 cm

1. Choose two spots, spot 1 and 2, in x and

y direction. Or we can choose two spots
along any direction
2. By measurement, we know r1=1.10cm,
r2=0.65 cm, and =90 , calculate
r1:r2=d2:d1=1.10:0.65=1.69
3. List the ratios of d from the allowed (hkl)
according to the structure factor rule. Put
these ratios into a table. For fcc, the allowed
diffraction planes are (111), (200), (220),
(311), (222), (400). Start from the low order
planes.

CHEM 793, 2008 Fall

Ratios of d-spacings from allowed diffraction planes (d1/d2)

{hkl}

d2

111

200

220

311

222

400

d1

h2+k2+l2

11

12

16

111

200

220

311

11

222

12

400

16

1
1
1
1
1
1

CHEM 793, 2008 Fall

4. Calculate all ratios of d-spacings from the allowed diffraction planes.

5. It was found that three ratios, 1.633, 1.658 and 1.732, are close the measured ratio: 1.69
6. Check the measured angle between vector r1 and r2 is 90. The planes {311}, {200} and {222} can be
removed, since no such planes at 90.
7. Only {111} and {220} are left. We choose (h2k2l2)=(-111) and (h1k1l1)=(220), so that their angle is
90.

Ratios of d-spacings from allowed diffraction planes (d1/d2)

{hkl}

h2k2l2

111

200

220

311

222

400

11

12

16

1.732

2.828

3.31662

3.464

0.866

0.612

0.52223

0.5

0.433

0.707

0.60302

0.577

0.5

0.8528

0.816

0.707

0.957

0.829

h^2+k^2+l^2
h1k1l1

h^2+k^2+l^2

111

1.73205081

200

1.155

220

2.82842712

1.633

1.414

311

11

3.31662479

1.915

1.658

1.173

222

12

3.46410162

1.732

1.225

1.04447

400

16

2.309

1.414

1.20605

CHEM 793, 2008 Fall

1
1.155

0.866
1

@ Measure r1=1.10cm, r2=0.65 cm, and =90 ,

calculate r1:r2=d2:d1=1.10:0.65=1.69
8. Label (-111) and (220) in diffraction pattern.
9. Using vector addition to index other spots
10. Calculate the zone axis from the vector cross
product.
(-3-11)

(-111)

(131)

r2= 0.65 cm
r1=1.10 cm
(220)
(-2-20)

11. Several excellent computer programs are available

to help indexing the diffraction patterns (such as EMS,
Desktop Microscopist)

Zone axis [uvw] :

(000)

a
[uvw ] = [ 220 ] [111] = 2
1

b
2
1

(-1-3-1)

(1-1-1)

(31-1)

A FCC [1-12] diffraction pattern

c
0
1

= ( 2 0) a + (0 2) b + ( 2 + 2) c

= [ 2 2 4 ] = [11 2 ]
CHEM 793, 2008 Fall

Kinematical Simulation of
Aluminum

On-line simulation is
available at
http://emaps.mrl.uiuc.edu/
CHEM 793, 2008 Fall

4.5mm

90

11.0 mm

HW#14, Index the diffraction patterns from a bcc crystal and find the zone axis of this
pattern.
Due day: 10/20/08

CHEM 793, 2008 Fall

The following figures are some the most useful diffraction patterns for bcc and fcc crystal.
More diffraction patterns of other types of crystals can be found in crystallography handbook.
Keep the handbook in hand when you are using a TEM to study the crystal specimen.
In addition, we can use the reciprocal rule to assist understanding the bcc and fcc patterns.
This rule is very useful in practice. We can very quickly identify the diffraction direction, i.e.
beam direction.
bcc real space -- fcc reciprocal space
fcc real space -- bcc reciprocal space
B1

e.g.
A1

C1
D1

B2
C2

So [001] diffraction pattern is to

extend the reciprocal plane of
reciprocal lattice unit cell,
A1B1C1D1, also see the standard
bcc [001] pattern.
B1

C1

A1

D1

A2
bcc in real space

D2
fcc in reciprocal space

The corresponding
reciprocal lattice is a fcc

CHEM 793, 2008 Fall

Reciprocal plane
A1B1C1D1 in unit cell

Reciprocal plane
B1B2D21D1 in unit cell

CHEM 793, 2008 Fall

Four standard indexed

diffraction patterns for
bcc crystals in [001],
[010], [-111], and [112]. Ratios of the
principal spot spacings
are shown as well as
angles between the
principal plane
normals. Forbidden
reflection spots are
indicated by x.
The [001] pattern is
obtained by extending
A1B1C1D1 reciprocal
plane in reciprocal
lattice unit cell,
considering the
structure factor.
Similarly, the [110]
pattern is obtained by
extending B1B2D2D1
reciprocal plane in
reciprocal lattice unit
cell.

Four standard
indexed diffraction
patterns for fcc
crystals in [001],
[010], [-111], and [112]. Ratios of the
principal spot
spacings are shown
as well as angles
between the principal
plane normals.
Forbidden reflection
spots are indicated
by x.

CHEM 793, 2008 Fall