CHEM 793, 2008 Fall

Chapter 3
Basic Crystallography and Electron Diffraction from Crystals
Lecture 14
CHEM 793, 2008 Fall
Announcement
Midterm Exam: Oct. 22, Wednesday, 2:30 4:30
CHEM 793, 2008 Fall
( )

+ +
=
i
lz ky hx i
i hkl
i i i
e f F
2
HW#11: Prove the 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.
Due day: 10/13/08
( ) ( )
{ }
odd and even mixed are l k, h, if , 0
odd all or even all are l k, h, if , 4
1 so
2
1
,
2
1
, 0 ,
2
1
, 0 ,
2
1
, 0 ,
2
1
,
2
1
, 0 , 0 , 0 z y, x,
is vector basis the fcc, for
) ( ) ( ) (
=
=
+ + + =
|
.
|

\
|
|
.
|

\
|
|
.
|

\
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=
+ + +
F
f F
e e e f F
l k i l h i k h i
D1
B2
CHEM 793, 2008 Fall
HW#12: Fe3AlC phase in Fe-C-A system has a cubic structure: Al is corner, C is in the cubic center, and Fe is in the center of
each face.
1. Derive an expression for the structure factor in terms of f
Al
, f
Fe
, and f
C
2. Sketch the (100)* section of the reciprocal structure for this Fe3AlC phase, labeling the low index diffractions and indicating
relative intensities.
C
Al
Fe
( ) ( ) ( )
| |
obtained be can pattern n diffractio the factor, structure on the Based
planes n diffractio order low as {020} and {011},
{001}, take structure, reciprocal * (100) sketch To
: (hkl) in even 1 and odd 2
: (hkl) in odd 1 and even 2
3 : odd l k, h,
3 : even l k, h,
f F
1/2) 1/2, (1/2, at C
and ), (0,1/2,1/2 ), (1/2,0,1/2 ), (1/2,1/2,0 at Fe (0,0,0), at Al
) (
Al
Fe C Al
Fe C Al
Fe C Al
Fe C Al
k l i l h i k h i
Fe
l k h i
C
f f f F
f f f F
f f f F
f f f F
e e e f e f
+ =
=
+ =
+ + =
+ + + + =
+ + + + +
000 010 020
001
002
011 021
0-11
0-10
0-20
0-21
00-1
hkl all even strong intensity
hkl two odd and one even,
moderate intensity
hkl two even and one odd, low
intensity
0-1-1
01-1 02-1
0-2-1
00-2
CHEM 793, 2008 Fall
Indexing Diffraction Patterns
(a) A single perfect
crystal
(b) A small number of
grains- note that
even with three
grains the spots
begin to form circle
(c) A large number pf
randomly oriented
grains-the spots
have now merged
into rings
CHEM 793, 2008 Fall
1. Analysis of polycrystalline diffraction pattern--- ring pattern
Incident beam
Small grains
Diffracted beams
from (hkl) planes in
each particles
(hkl) ring
g
The geometry of formation of a
single (hkl) ring by accumulation
of (hkl) beams from different
grains.
Ring pattern from a fine grained
polycrystalline sample is in effect the
superposition of many single crystal
patterns.
The rings occurs in the characteristic
sequence, regarding different d
hkl
CHEM 793, 2008 Fall
The geometry of formation of a single (hkl) ring by accumulation (or superposition) 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 pattern would look more like that shown in Fig. b.
a
b
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
e.g.
bcc in real space
fcc in reciprocal space
A1
C1
B1
D1
D2
A2
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.
A1
B1 C1
D1
The corresponding
reciprocal lattice is a fcc
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.
Reciprocal plane
A1B1C1D1 in unit cell
Reciprocal plane
B1B2D21D1 in unit cell
CHEM 793, 2008 Fall
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
Application of Electron Diffraction
Determining orientation relationship between crystals
Advantage of TEM: image and diffraction pattern can be obtained simultaneously
(a) A TEM Dark Field micrographs showing Fe2TiSi precipitated after ageing in -Fe,
(b). The corresponding SAD pattern of -Fe (bcc, a=2.866A, strong spots) and
Fe2TiSi precipitates ( fcc, a=5.732A, weak spots) in a single crystallographic
orientation. The camera length is 31.5 Amm here.
(a) (b)
CHEM 793, 2008 Fall
fcc
fcc
bcc
Refer to the standard pattern
and measure the distances and
angles between spots
CHEM 793, 2008 Fall
The patterns of -Fe and Fe2TiSi can be indexed as shown above, we can find:
(200) of Fe2TiSi is half distance of (200) -Fe , therefore twice d-spacing of -Fe
from center.
These planes are therefore parallel and the lattice parameter of Fe2TiSi is twice
that of -Fe .
Similarly, the (022) Fe2TiSi reflection is coincident with (011) -Fe
The zone axes, obtained by cross product of vectors, are both [0-11]
Therefore the orientation relationship may be specified by quoting the parallelisms:
(200)Fe2TiSi//(200) -Fe and zone axis: [0-11]FeiTiSi//[0-11] -Fe
(022) Fe2TiSi
coincident with
(011) -Fe
CHEM 793, 2008 Fall
(022) Fe2TiSi
coincident with
(011) -Fe
Other, more complicated, orientation relationships may be determined by
the same simple approach, but to go from the parallelism between the
planes and zone axes between planes not observed in the patterns (i.e.
those that are not on Laue condition or not nearly parallel to the electron
beam direction), requires a knowledge of the stereographic projection.
CHEM 793, 2008 Fall
Stereographic Projection
Nomenclature of Crystallographic Directions and Face normals / poles
Indices (no brackets, parenthesis) for directions
CHEM 793, 2008 Fall
(0-11)
(011)
(100)
(-100)
(01-1)
Stereographic Projection
Stereographic projections are 2-D
maps of the orientation
relationships between different
crystallographic directions.
They are useful for representing
the electron diffraction pattern,
although stereographic projections
were developed for representing 3-
D crystallography.
(001)
(00-1)
(010)
(0-10)
CHEM 793, 2008 Fall
3-D construction of Stereographic Projection
To construct a stereographic projection, begin
with a tiny crystal situated at the center of a large
sphere
Conventional terminology calls the normals to
crystallographic planes, poles. We specify the
poles pointing upwards to the north pole of the
sphere.
In figure, nine poles were extended from the
crystal and intersect the sphere.
We use the points of intersection to create a [001]
stereographic projection.
To project these intersection points onto a 2-D
surface, first draw straight lines from the
intersection points to the south pole. Next, mark
with an X the points of intersection of these lines
on the equatorial plane of the sphere.
The stereographic projection is the equatorial
plane of the sphere with these marked
intersections, X points.
The stereographic projection contains orientation
information about all poles that intersect the
northern hemisphere of the sphere.
Poles such as (01-1) and (00-1), which intersect
the southern hemisphere of the sphere, are not
included in the [001] stereographic projection.
However, the entire southern hemisphere of the
crystal can be obtained by rotating the [001]
stereographic projection by 180, and changing
the signs of all poles indices
(0-11)
(011)
(100)
(-100)
(01-1)
(001)
(00-1)
(010)
(0-10)
CHEM 793, 2008 Fall
Stereographic Projection
2-D description of construction of
Stereographic Projection
Section through sphere of projection
showing relation of spherical poles (E, D) to
stereographic poles (E, D)
CHEM 793, 2008 Fall
Stereographic Projection
Relation of spherical
and stereographic
projections
Equatorial plane as
projection plane
South pole as projection pole
Face poles
CHEM 793, 2008 Fall
Stereographic projection
(equatorial plane) of
some cubic crystal faces
[001] is zone axis, and all
poles on the great circle
(such as (010), (100), etc.)
belong to this zone axis,
e.g. [-1-10]. [001]=0,
[110].[001]=0, etc., i.e.
(hkl) is normal to [vuw]
Stereographic Projection
CHEM 793, 2008 Fall
Relationship between stereographic projections and electron diffraction patterns
In the high energy electron diffraction, the Bragg
angles are so small that the incident electron beam
travels nearly parallel to the diffracting planes.
When the electrons travel down the crystal from the
north pole of a spherical projection, the diffractions
occurs from planes whose poles intersect the
equator of the sphere, perhaps within a degree or
so (Zone Law).
-111 || -222
(-112) (002)
(000) (-110) (1-10)
(1-12)
-112
001
110
1-12
1-10 -110
(-22-2)
(-222)
(00-2) (-11-2)
(1-1-2)
1-1-1
-112
1-1-2
00-1
Orientation relationship between bcc [110] diffraction pattern at left, and [110] stereographic projection at right.
Angles between the vectors are the same on the left and right sides
The figures show a bcc crystal
oriented with its [110] direction
pointing upwards towards the electron
gun
CHEM 793, 2008 Fall
Relationship between stereographic projections and electron diffraction patterns
In relating stereographic projections to the diffraction planes, it is
important to remember that stereographic projections contain no
information about the distances between the diffraction spots,
and contain no information about structure rules. Nevertheless,
the angles between the vectors in diffraction pattern and in the
stereographic projection are the same, e.g. although {111}
diffraction are forbidden for bcc crystals, the (--222) diffraction
occurs at the angle of the [-111] direction
-111 || -222
(-112) (002)
(000) (-110) (1-10)
(1-12)
-112
001
110
1-12
1-10 -110
(-22-2)
(-222)
(00-2) (-11-2)
(1-1-2)
1-1-1
-112
1-1-2
00-1
Orientation relationship between bcc [110] diffraction pattern at left, and [110] stereographic projection at right.
Angles between the vectors are the same on the left and right sides
The figures show a bcc
crystal oriented with its [110]
direction pointing upwards
towards the electron gun
CHEM 793, 2008 Fall
Manipulations of stereographic projections
The stereographic projection is a powerful tool for working problems that involve orientations
between two different crystals. We introduce a tool analogous to a protactor, called Wulff Net,
to do easily so. Wulff Net is a projection of lines of latitude (measuring north-south position)
and longitude (measuring east to west position) obtained from a calibrated reference sphere.
The lines of latitude are arcs in the stereographic projection, as are the lines of longitude, but
the lines of longitude are concave inwards.
Wulff Net named after G.V. Wulff, Russian crystallographer (1863-1925)
Great cycles and small cycles are drawn at intervals of 2
CHEM 793, 2008 Fall
The Wulff Net
should be
photocopied onto
a transparency for
work with the
matching
stereographic
projections
CHEM 793, 2008 Fall
0
10
20
30
40
50
60
70
80 90
20
30
40
60
70
80
10
50
90
0
10
20
30
40
50
60
70
80
10
20
30
40
50
60
70
80
CHEM 793, 2008 Fall
CHEM 793, 2008 Fall
Wulff net is a tool to rotate a crystal into any 3-D orientation. Simple rotations include
rotation about the center of the projection and about the north-pole of the net
Examples:
1. Find the angle between two planes
(a). Poles are on the edge of the stereographic edge: 1 operation: just overlay the
Wulff Net in any orientation, and count the tick marks on the edge, Figure (a).
(b). One pole is in the center of the projection, and the other is at an arbitrary position:
1 operation: Align the Wulff Net with its equator passing through the two points and
count the longitude tick marks along the equator.
001
-112
Angel between (-112)
and (001) or (002)=35
[110] projection [001] projection
001
-112
(a)
CHEM 793, 2008 Fall
Examples:
1. Find the angle between two planes
(b). One pole is in the center of the projection, and the other is at an
arbitrary position: 1 operation: Align the Wulff Net with its equator passing
through the two points and count the longitude tick marks along the equator.
[001] projection
001
-112
Equator of Wulff
net
Angel between (-112)
and (001) or (002)=35
CHEM 793, 2008 Fall
Examples.
2. Find the angle between two arbitrary poles.
1 operation: Orient the Wulff Net so that the two points are intersected by a common line of
longitude, and count the latitude ticks along the line of longitude.
Pole 1
Pole 2
Angel between pole 1
and pole2 =20
Pole 1
Pole 2
CHEM 793, 2008 Fall
Examples.
3. Find a [010] stereographic projection from an [001] stereographic projection
When the indices of the new stereographic projection are obtained from the old by
cyclic permutation, just make transformation xyz into yzx. E.g. the poles 100 and 010
on the edge of the old [010] projection become 001 and 100 in the new [010] projection.
We can confirm that [001]X[100]=[010], by right hand rule g3=g1Xg3
g1
g2
g3
CHEM 793, 2008 Fall
Examples.
4. Find a new [113] stereographic projection from an [001] stereographic projection
1 operation: Orient the Wulff net so that its equator passes through the 113 pole in the
[001] projection. Then move the 113 pole into center along equator, and move all other
poles of the [011] projection along lines of latitude by same angle. Note the
appearance of the hkl pole at the bottom of the projection, and the disappearance of
the h-k-l at the top.
113
-h-k-l
hkl
113
-h-k-l
hkl
CHEM 793, 2008 Fall
Examples.
4. Find a new [113] stereographic projection from an [001] stereographic projection
1 operation: Orient the Wulff net so that its equator passes through the 113 pole in the
[001] projection. Then move the 113 pole into center along equator, and move all other
poles of the [011] projection along lines of latitude by same angle. Note the
appearance of the hkl pole at the bottom of the projection, and the disappearance of
the h-k-l at the top.
113
-h-k-l
hkl
113
-h-k-l
hkl
-h-k-l is out and disappears
from new [113] projection
CHEM 793, 2008 Fall
Examples.
5. Rotation of a crystal about an arbitrary pole: You are given one crystal with a [110]
projection. A second crystal is then given a 10rotation about its (100) pole. On the
projection of the first crystal, where is the poles of the second crystal after this rotation?
3 operations: 1). Move the pole (100) into center of the projection by moving it along the
equator of the Wulff Net. This generates a [100] projection, with the typical pole x moved
along a line of latitude to position x.
110
100
x
[110] projection
100
100
X
[100] projection
X
CHEM 793, 2008 Fall
Examples.
3 operations: 2). Rotate the [100] projection about its center by 10.
Point x moves to position x; 3). Rotate the (100) back to its original
position, moving it along the equator or the Wulff Net. Point x moves
along a line of latitude to point x
100
X
[100] projection
X
100
X
[110] projection
X
10
CHEM 793, 2008 Fall
Examples.
3 operations: 2). Rotate the [100] projection about its center by 10. Point x
moves to position x; 3). Rotate the (100) back to its original position, moving it
along the equator of the Wulff Net. Point x moves along a line of latitude to point
x
100
[100] projection
X
100
[110] projection
X
X
CHEM 793, 2008 Fall
Examples.
7. (*** extra information, you dont need fully understand) Kurdjumov-Sachs (K-S)
orientation relationship between bcc and fcc crystals. The K-S relationship specifies the
parallel planes: (1-10)bcc || (-111)fcc and the parallel directions in these plans: [111]bbc ||
[110] fcc
3 operations: 1). Use the [110] stereographic projection to the point the [110]fcc direction
upwards, and [111] stereographic projection to [111] bcc direction upwards.
[110] fcc
[110] fcc projection
(1-11) fcc
(1-1-1) fcc
(-111) fcc
(-11-1) fcc
(1-12) fcc
(-11-2) fcc
(00-1) fcc
(001) fcc
[111]
bcc
[111] bcc projection
(01-1) bcc
(-110) bcc
(1-10) bcc
(0-11) bcc
(11-2) bcc
(-1-12) bcc
(10-1) bcc
(-101) bcc
CHEM 793, 2008 Fall
Examples.
3 operations: 2). Overlay it with the [111] stereographic projection so that [111] bcc is
parallel with [110]fcc direction.
[110] fcc
[110] fcc projection
(1-11) fcc
(1-1-1) fcc
(-111) fcc
(-11-1) fcc
(1-12) fcc
(-11-2) fcc
(00-1) fcc
(001) fcc
[111]
bcc
[111] bcc projection
(01-1) bcc
(-110) bcc
(1-10) bcc
(0-11) bcc
(11-2) bcc
(-1-12) bcc
(10-1) bcc
(-101) bcc
fcc
bcc
CHEM 793, 2008 Fall
Examples.
3). Rotate the two overlain projections so that the(-111)fcc pole on the edge of projection is
on top of the [1-10]bcc pole.
We see that a <112> direction is parallel in both crystal
[111] bcc
(01-1) bcc
(-110) bcc
(1-10) bcc
(0-11) bcc
(11-2) bcc
(-1-12) bcc
(10-1) bcc
(-101) bcc
fcc
bcc
[110] fcc
(1-11) fcc
(1-1-1) fcc
(-111) fcc
(-111) fcc
(1-12) fcc
(-11-2) fcc
(001) fcc
(00-1) fcc
Some poles of overlain
[111]bcc and [110]fcc
stereographic projections
CHEM 793, 2008 Fall
Examples.
K-S orientation relationship between bcc and fcc crystal
An experimental result of Fe-9Ni steel shows the (002) fcc diffraction is isolated from the
bcc diffraction. We can locate small amounts of fcc phase within bcc matrix using this
diffraction spot for a DF image.
CHEM 793, 2008 Fall
Example
Using the [001] stereographic projection provided, sketch and label the (221)*
section of reciprocal space for fcc crystal.
1. First determine the necessary rotation to bring [221] to center. This can be
calculated as follows:
o
70
1
] 001 [
9
] 221 [
arccos =
)
`

=
2. To make the [221] projection, we need to rotate every point by 70. To
simplify the operation, we only select the points which will end up on the
outside edge of [221] projection, i.e. (hkl) satisfies 2h+2k+l=0. So we can
visually guess the following poles: [-110],[1-10],[-322],[-212],[1-22],[-102],[0-
12] etc.
3. For fcc, h,k,l all even or odd, so we choose even multiples of <-110>,<-
212>,<1-2,2>,<-102>, and <0-12>. All these points in [001] projection should
be rotated 70along their latitude to get [221] projection.
CHEM 793, 2008 Fall
Move 70
CHEM 793, 2008 Fall
(-110)
(1-10)
(-212)
(-102)
(0-12)
CHEM 793, 2008 Fall
Considering the structure factor, use even multiples all poles, and re-
arrange the spots according to ratios and angles
(-220)
(2-20)
(-424)
(0-24)
(-110)
(1-10)
(-212)
(-102)
(0-12)
: Forbidden spots
(4-40)
(-440)
(-204)
71.6

Schematically drawing of [211] diffraction

CHEM 793, 2008 Fall
The tedious Wulff net operation can be performed by several computer
programs ( such as EMS, Desktop Microscopist, and CrystalKit, etc.)
[001] Pole projection
CHEM 793, 2008 Fall
[211] Pole projection ( low order pattern)
CHEM 793, 2008 Fall
[211] Pole projection ( high order pattern). fcc pattern is obtained
excluding the forbidden spots
CHEM 793, 2008 Fall
HW# 12 Use two Wulff Nets to solve this problem.
In geoscience, one nautical mile is defined as one minute of arc along a great circle
of the earth. So one degree arc along a great circle is equal to 1x60 min.=60 nautical
mile. Based on the world map, we know Las Vegas, US, is at 36 degree north
latitude, 115 degree west longitude. Beijing, China, is at 40 degree north latitude,
116 degree east longitude. How many nautical miles is Beijing from Las Vegas?
Please briefly describe the operations you had to perform.
Due: Oct. 27, 08.
CHEM 793, 2008 Fall
Beijing
CHEM 793, 2008 Fall
Las Vegas
CHEM 793, 2008 Fall
Next Lecture:
Kikuchi Line and its indexing
Double diffraction
CBED pattern (convergent beam electron diffraction)