Reciprocal Lattices and Diffraction

Suggested
gg
Reading
g
Chapter 6, M. DeGraef and M.E. McHenry, Structure of Materials, Cambridge (2007).
Appendix A from Cullity & Stock

Many physical properties of crystals as well

as the geometry of the three
three-dimensional
dimensional
patterns resulting from a diffraction event
are most easily represented using the
concept of the reciprocal lattice!
Diffraction occurs in inverse proportion
to the spacing between objects causing
diffraction
2

Reciprocal Lattice
Vector representation of directions and
interplanar spacing of diffracting planes.
Real Space:
a,
a b,
b c,
c , ,
Reciprocal Space: (just another type of lattice)
a*,
* b*
b*, c*,
* *,
* *,
* *
3

Reciprocal Lattice
(FCC)
0,0,2
2,0,2

022
0,2,2

c* 2,2,2

1,1,1

b*

a*
0,0,0
2,0,0

Real Space

0,2,0
2,2,0

Reciprocal Space

Recall simple vector operations

Dot product (scalar product):
x y x y cos

z
y

h2 k 2 l 2

h2 k 2 l 2

Cross product (vector product):

x y z x y sin
i

z is the direction x y plane

Useful Properties of the reciprocal lattice

c
*

a b
c a b

area of base

unit cell volume

1

height
1

d001
For orthogonal crystals,

c*

c
B

b
O a

C
A
z

d001 in
real
space

Plane normal
to (001)

y
x

1
1
*
c
d001
c
6

We can define reciprocal lattices

F
For an arbitrary
bit
llattice
tti [a
b c and
d
( 90)] in
i
real space.
b c
b c

a*

a b c
V
c a
c a

b*

b c a
V
a b
a b

c*

c a b
V

c**

c
b*

b
O

a
a*

V unit cell volume a b c b c a c a b

a* bc plane in real space; it is the reciprocal lattice vector for a
b* ac plane in real space; it is the reciprocal lattice vector for b
c* ab plane in real space; it is the reciprocal lattice vector for c

Useful Properties of the reciprocal lattice contd

1
*
a ;
a

cos cos cos

cos
sin sin

1
*
b ;
b

cos cos cos

cos
sin sin

1
1
*
c
c ;
d001 c

cos cos cos

cos
sin sin

a
*

b
*

1
d100
1
d010

For
orthogonal
crystals
8

Relationship between real and reciprocal

In orthogonal real lattices
(a= b = c and = = (= 90))

a* a; b* b; c* c
Not necessarily so in non-orthogonal
non orthogonal lattices
We can draw an analogy
gy between reciprocal
p
and real lattices:
ruvw ua vb wc
We use this to build a real lattice from unit cells
rhkl* ha* kb* lc*
We can use this to build a reciprocal lattice

Construction of a 2D reciprocal lattice

01

10

(a) draw the plane lattice and mark the unit cell
Adapted from R. Tilley, Crystals and Crystal Structures,
John Wiley & Sons, Hoboken, NJ, 2006

10

Construction of a 2D reciprocal lattice

Adapted from R. Tilley,
Crystals and Crystal
Structures, John Wiley &
Sons, Hoboken, NJ, 2006

00

01

b*

10

a*

(b) draw lines perpendicular to the two sides of the unit cell to give the axial
directions of the reciprocal lattice basis vectors.
11

Construction of a 2D reciprocal lattice

Adapted from R. Tilley,
Crystals and Crystal
Structures, John Wiley &
Sons, Hoboken, NJ, 2006

00

01

b*

10

a*

Sets axes and

interaxial
angle

What youre doing first is finding the spacing between

the planes making up the unit cell sides.

(c) determine the perpendicular distances from the origin of the direct lattice to the
end faces of the unit cell, d10 and d01, and take the inverse of these distances, 1/d10
and 1/d01, as the reciprocal lattice axial lengths, a* and b.

12

Construction of a 2D reciprocal lattice

Adapted from R. Tilley,
Crystals and Crystal
Structures, John Wiley &
Sons, Hoboken, NJ, 2006

00

1
a* *
d 01
10

b* 1 / d 01
01

Draw
reciprocal
lattice using
axes
a* = 1/d10
a
b* = 1/d01

T k reciprocals
Take
i
l tto gett reciprocal
i
l llattice
tti parameters.
t
(d) mark the lattice points at the appropriate reciprocal distances, and complete the
lattice.

13

Construction of a 2D reciprocal lattice

Everyy p
point on a
reciprocal lattice
represents a set of
planes in the real
space crystal!

Adapted from R. Tilley,

Crystals and Crystal
Structures, John Wiley &
Sons, Hoboken, NJ, 2006

00
00

01

a
10

11

Real lattice

1
a*
d 01
10

b* 1 / d 01
01
1

d11

11

Reciprocal lattice

The vector joining the origin of the reciprocal lattice to a lattice point hk is
perpendicular to the (hk) planes in the real lattice and of length 1/dhk.

14

c*

a*
d 001

(a)

d100

(b)
c*

c**

102

a*

101

c* 1 d 001 *
a* 1 d100

100
10 1

(d)

(c)

002
001
000

b* 1 d 010
010

020

(e)

030

100

102

101
*

302

201

001

000

100

00 1

10 1

200

301

401
401

300

20 1

30 1

400
40 1

a*

Figure 2.10 The construction of a reciprocal

l tti (a)
lattice:
( ) the
th a-c section
ti off the
th unit
it cell
ll in
i a
monoclinic (mP) direct lattice; (b) reciprocal
lattice aces lie perpendicular to the end faces
of the direct cell; (c) reciprocal lattice points
aree spaced
ed a** = 1/d100 andd c** = 1/d001; (d)
the lattice plane is completed by extending
the lattice; (e) the reciprocal lattice is
completed by adding layers above and below
the first plane.
plane

200
012

011
110

002

202

Construction of a 3D
reciprocal
p
lattice

Adapted
p
from R. Tilley,
y Crystals
y
and Crystal
y
Structures,
John Wiley & Sons, Hoboken, NJ, 2006

210

Just like 2
2-D
D
15

Cubic Reciprocal Lattice

b*
b

0.25 -1

040

(010)

(110)

(210)
c

020

a
[010]

4
REAL LATTICE

ruvw ua vb wc

c*

90
90

020 120

220

010 110

210

[110]

[210]

a*
200

400

RECIPROCAL LATTICE

r hkl* ha * kb * lc *

Every point on a reciprocal lattice represents a

set of planes in the real space crystal!
Reciprocal lattice vectors are 90 away from real
space planes!

16

Importance of Reciprocal Space

When a diffraction event occurs, the diffracted
waves/pattern will match
match the reciprocal lattice.
Radiation scatters
scatters in inverse proportion to the
spacings between diffraction centers (i.e., planes in
crystals).
We make the use of this fact in x-ray
y diffraction and
transmission electron microscopy.

17

Why use reciprocal space

Braggs Law:

(Defines conditions where a crystal is oriented for coherent scattering)

n 2d sin
We can combine n and d as follows:

d
d hkl
n
Thi allows
This
ll
us to
t write
it B
Bragg's
' Law
L
as:

2d hkl sin hkl

sin hkl

1
opposite
/ 2 d hkl

2
d hkl
hypotenuse

(Simple geometric proof on vg #226)

18

sin hkl

1
opposite
BC
/ 2 d hkl

2
d hkl
hypotenuse AC
h

Ewald Sphere
Construction

Reflection or
Ewald sphere

Limiting sphere

A
CRITICAL
Only lattice points lying
within the limiting
g sphere
p
can diffract. Points lying
on the Ewald sphere will
satisfy the Bragg
condition.

hkl

2hkl

1
*
dhkl
dhkl
C (0,0,0)

1
2

Origin
g of
reciprocal lattice
and center of
limiting sphere

See this web site for an explanation and example

http://www.msm.cam.ac.uk/doitpoms/tlplib/xray-diffraction/ewald.php
19

Ewalds Sphere Construction

Graphical representation of Bragg

Braggss Law in reciprocal space
space.
s/

Incident
wave

so

so

Incident
wave

s so g d *

so /

REAL SPACE

hkl

O
g is the
diffraction
vector

RECIPROCAL SPACE

Consider incident waves of radiation (i.e., X-rays) moving in a direction so,

fl ti off
reflecting
ff off crystallographic
t ll
hi planes
l
in
i a direction
di ti s.
Let point O represent the origin of the reciprocal lattice.
Draw a circle of radius 1/ w/ center, A, on CO but passing through O.
Rotation of crystal rotates the reciprocal lattice about O. This will bring
different reciprocal lattice points into contact w/ Ewalds sphere.
20

 s so

Ewalds sphere

2sin

To satisfy Bragg's Law:

s so
1
*
d hkl

d hkl
1
d
sin hkl Bragg's Law
2

*
d 130

Crystalline
C
t lli
solid

so

*
d 030

*
d130

*
d 230

*
d 020

*
d120

*
d 220

*
d 010

*
d110

*
d 210

*
d100

*
d 200

(0,0,0)

d 0*10

RECIPROCAL SPACE

My original way to show it.

it
Next page is better.

Size of sphere
p
corresponds
p
to wavelength
g of radiation used
(see next page).
Rotation of the crystal will cause points to lie on the sphere.
When points lie on the sphere, Braggs law is satisfied!
21

Ewalds sphere

OB OB
sin

CO 2 /
Which can be re-written as:
C
1
2
sin
OB
Since B is a reciprocal lattice point:
1
*
OB
d hkl
g
d hkl

so
Crystalline
C
t lli
solid

1
d hkl and 2d hkl sin
OB
[Braggs Law]

*
d 130

*
d 030

*
d130

*
d 230

*
d 020

*
d120

*
d 220

*
d 010

*
d110

*
d 210

*
d100

*
d 200

(0,0,0)

A 1

d 0*10

RECIPROCAL SPACE

Size of sphere
p
corresponds
p
to wavelength
g of radiation used
(see next page).
Rotation of the crystal will cause points to lie on the sphere.
When points lie on the sphere, Braggs law is satisfied!
22

If you change ,
you change the
radius of the
Ewalds sphere.
This is how the
Laue technique
works.
works
Diffractometers
generally use
fixed and
variable .
Reflecting sphere for
smallest wavelength

Reflecting sphere for

largest wavelength

C. Hammond, The Basics of Crystallography and Diffraction, 3rd Ed., Oxford

University Press, Oxford, UK, 2009, p. 201.

23

A.D. Krawitz, Introduction to

Diffraction in Materials
Science and Engineering
Engineering,
Wiley, New York, 2001

0
0

Increasing diffraction angle

Diffractometers generally use fixed

and variable .

24

Synopsis
1. The reciprocal lattice allows us to compute the spacing
between successive lattice planes in a crystal lattice.
2. The reciprocal lattice vector d*hkl with components (hkl) is
perpendicular to the plane with Miller indices (hkl).
3. The length of the reciprocal lattice vector is equal to the
inverse of the spacing between the corresponding planes.
4. Diffraction
iff i off X-rays (and
( d electrons)
l
) is
i described
d
ib d by
b the
h
Bragg equation, which relates the radiation wavelength () to
g ()
( ) and the spacing
p
g between crystal
y
the diffraction angle
planes (dhkl).

25

Diffraction and the Recripocal Lattice

Suggested Reading
1 Chapters 11-14
1.
11 14, M
M. DeGraef and M
M.E.
E McHenry
McHenry, Structure of Materials,
Materials
Cambridge (2007).
2. Chapter 7, Pecharsky and Zavalij, Fundamentals of Powder Diffraction and
Structural Characterization of Materials, 2nd Edition, Springer (2009)

26

Electromagnetic (EM) Radiation

Self-propagating
S
lf
i waves with
ih
perpendicular electric and magnetic
components

http://en.wikipedia.org/wiki/File:Onde_electromagnetique.svg

27

Properties of Electromagnetic Waves contd

E photon of energy h

hc

h Planck's constant 6.626 10

34

Js

frequency of the wave

c speed
d of
f light
li ht 3.00
3 00 108 m/s
/

wavelength of radiation
28

Visible Light:
g
~6000
X-rays: ~0.5 2.5
Electrons: ~0.05

http://en.wikipedia.org/wiki/File:EM_Spectrum_Properties_edit.svg

29

http://en.wikipedia.org/wiki/File:EM_Spectrum_Properties_edit.svg
30

Scattering of EM Radiation by Crystals

For a material to yield a diffraction pattern, the EMR
wavelength lattice spacing.
Neutrons
Electrons
X-rays

X-radiation is scattered (i.e., absorbed + re-emitted):

Elastic (little or no energy loss diffraction peak)
Inelastic (energy loss no diffraction peak)
31

Laues Equations
When scattering occurs there is a change in the path of the
incident radiation.
Diffracted
beam

n path difference between incident and

scattered beams.

x a (cos
( cos o ) a ( S So ) h
y b(cos cos o ) b( S So ) k
z c(cos
( cos o ) c( S So ) l
[h, k , l are integers]

o
So

Incident
beam

Constructive interference occurs when all 3 equations are

satisfied simultaneously.
simultaneously
32

Braggs Law

path difference AB BC 2d sin

For constructive interference n

2d sin n
d
d hkl
n
2d hkl sin (or n 2d sin )

33

Braggs Law
Braggs la
law can be expressed
e pressed in vector
ector form as:
*
S So 2sin d hkl
*
d hkl

hkl
*
d hkl

1
d hkl

Incident
beam

So

Thus:
S So

-So
S-So

*
d hkl
lc *
hkl ha * kb * lc

Diffracted
b
beam

Trace of (hkl)
reflecting plane

This tells us that constructive interference occurs when

SSo coincides with the reciprocal lattice vector of the
reflecting planes.

Ref p. 61 in text

34

Laues Equations and the Reciprocal Lattice

We
W can representt the
th Laue
L
equations
ti
graphically.
hi ll
Similar to Ewalds sphere.
For diffraction to be
observed (i
(i.e.
e Bragg
Braggs
s
law satisfied) S must
end on a reciprocal
lattice point.
point
Points satisfying this criteria
represent planes that are oriented
for diffraction

d h*kl

S So

(13)

(01)

(11)

(00)

(10)

So

(10)

Reflecting sphere

Braggs law, which describes diffraction in terms of scalars, is

generally used for convenience.

35

Diffracted
beam

*
hkl

S So

(13)

Limiting sphere
RADIUS = 2So/

INCIDENT
BEAM

(01)

(11)

(00)

(10)

So

Reflecting
sphere

(10)

To
satisfy
Braggss
Bragg
law
So
S
*
d hkl

n 2d sin
*
d hkl
g

1 2 sin

d
n
36

Reciprocal Lattice

The lattice constructed

from all diffraction
vectors (i.e., g) for a
crystal defines
possible Bragg
reflections.

Points that intersect

the reflecting sphere
will satisfy Braggs
law.

Changes in
wavelength ()
changes the circle
radius which can lead
radius,
to diffraction.
However, we generally
do not change .
000

Incident
beam

c*000 b*
a*

37

Reciprocal Lattice

A change in
orientation of the
incident beam relative
to the crystal changes
the orientation of the
reciprocal lattice,
reflecting sphere, and
limiting sphere.
Incident
beam

Change
g will eventuallyy
yield a condition where
diffraction is possible.

We mentioned this a
few lectures ago.

000

38

X-ray Diffractometer
X-ray source is generally
fixed.
Rotate sample and
detector to adjust /2.
/2
On instruments such as
our Bruker D8, the source
and detector move while
th sample
the
l remains
i
stationary.

Focal circle

Source

Detector

Fixed

Rotates on
focal circle

2
Sample

Rotates or remains stationary

Bragg Bretano
Bragg-Bretano
39

Braggs Law

path difference AB BC 2d sin

For constructive interference n

2d sin n
d
d hkl
n
2d hkl sin

40

Diffraction Directions
We can determine which reflections are allowed by
combining Braggs law with the plane-spacing
equations
q
for a crystals.
y
Cubic:
2d sin
sin 2

1
d2

k2 l2

2
4a 2

k2 l2

a2

This equation predicts, for a particular incident and

a particular cubic crystal of unit cell size a, all of the
possible Bragg angles for the diffracting planes (hkl)
41

Diffraction Directions contd

Example:
What are the possible Bragg angles for {111}
planes in a cubic crystal?
Solution:
3
sin 111 2 1 1 1 2
4a
4a
2

42

Diffraction Directions
What about other systems?
Tetragonal:

2d sin
sin 2

1
d2

k2

a2

c2

2 h2 k 2

4a 2

a2

l2
2
c

2 1

2
For 111 , sin 2 2 2

4 a
4a

Solution: must know c and a. Will be one p

peak.
What about {110}?
Ive intentionally given you a family here

43

Ewald s
Ewalds
Sphere

Diffraction
Cone

Incident
Beam

In powder diffraction you

generate an infinite
i fi i number
b off
randomly oriented, but identical,
reciprocal lattice vectors.
They form a circle with their
ends placed on the surface of
Ewalds sphere.
Theyy pproduce ppowder diffraction
cones at different Bragg angles
(see the next slide).

Debye
Ring

*
d hkl

So
S

Detector
*
R * g d hkl

1
d hkl

Adapted from Vitalij K. Pecharsky and Peter Y. Zavalij,

Fundamentals of Powder Diffraction and Structural Characterization
44
of Materials, Kluwer Academic Publishers (2005)

Adapted from Vitalij K. Pecharsky and Peter Y. Zavalij, Fundamentals of Powder Diffraction and
Structural Characterization of Materials, 2nd Edition, Kluwer Academic Publishers (2009), p. 154.

Ewalds
Ewald
s
sphere

*
d hkl

Incident
Beam

1
d hkl

So

Figure 8.2
45

Adapted from Vitalij K. Pecharsky and Peter Y. Zavalij, Fundamentals of Powder Diffraction and
Structural Characterization of Materials, 2nd Edition, Kluwer Academic Publishers (2009), p. 156.

Figure 8.4

In a linear diffraction pattern,

the detector scans through an
arc that intersects each Debye
cone at a single point; thus
giving
i i th
the appearance off a
discrete diffraction peak.
46

Exercises
1. Develop equations for the angles of diffraction for a
tetragonal (a = 3 , c = 9 ) crystal.

47