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Midterm Exam: Oct. 22, Wednesday, 2:30 4:30
000
000
000
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
KI
KD
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
h2k2l2
h3k3l3
(h1k1l1)
h1k1l1
000
A section
reciprocal
CHEM of
793,
2008 Fall lattice on (uvw)
=0
k1
k2
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
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
Using the structure factor rule to exclude the forbidden vectors from the candidate
reciprocal lattices
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)
2 d hkl sin = n
2 d hkl sin =
Diffracted beam
Incident beam
2
hkl
r: spot
distance
Q is samll
2 d
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
constant
L L
r=
=
d
a
r1
=
r2
h1 + k1 + l1
h2 + k 2 + l2
2
h2 + k 2 + l 2
d2
=
d1
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
(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.
Incident beam
Small grains
Diffracted beams
from (hkl) planes in
each particles
(hkl) ring
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.
a
Planar Ewald sphere
(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)
(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
(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
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
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.
r1
=
r2
h1 + k1 + l1
2
h2 + k 2 + l 2
d2
d1
Index procedure:
Angle: 90
0.65 cm
1.10 cm
{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
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
1
1.155
0.866
1
(-111)
(131)
r2= 0.65 cm
r1=1.10 cm
(220)
(-2-20)
(000)
a
[uvw ] = [ 220 ] [111] = 2
1
b
2
1
(-1-3-1)
(1-1-1)
(31-1)
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
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
C1
A1
D1
A2
bcc in real space
D2
fcc in reciprocal space
The corresponding
reciprocal lattice is a fcc
Reciprocal plane
A1B1C1D1 in unit cell
Reciprocal plane
B1B2D21D1 in 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.