Reciprocal Lattice Part of

MATERIALS SCIENCE
& AALearner’s Guide
Learner’s Guide

& ENGINEERING
AN INTRODUCTORY E-BOOK

Ewald Sphere Construction Anandh Subramaniam & Kantesh Balani

Materials Science and Engineering (MSE)
Indian Institute of Technology, Kanpur- 208016

 Reciprocal lattice. Reciprocal Email: [email protected], URL: home.iitk.ac.in/~anandh

http://home.iitk.ac.in/~anandh/E-book.htm
Crystal.
 Structure factor calculations.
 Ewald sphere construction. Diffraction Patterns
 Diffraction patterns.

 The concepts of reciprocal lattice, structure factor calculations (and sometimes Ewald
sphere construction) often ‘strike terror’ in the hearts of students.
 However, these concepts are not too difficult if the fundamentals are understood in 1D
and then extended to 3D.
ad these slides in parallel  Related
Relatedtopic:
topic:structure
structurefactor
factorcalculations
calculations(click
(clickhere)
here)
Related
Relatedtopic:
topic:X-ray
X-rayDiffraction
Diffraction(click
(clickhere)
here)
 Why study reciprocal lattices?
Reciprocal Lattice and Reciprocal Crystals
Often the concepts related to reciprocal lattice strikes terror in the minds of students. As we shall see this is not too difficult if concepts are first
understood in 1D.

 A crystal resides in real space. The diffraction pattern# resides in Reciprocal Space.
 In a diffraction experiment (e.g. powder diffraction using X-rays, selected area diffraction
in a TEM), a part of this reciprocal space is usually sampled.
 The diffraction pattern from a crystal (in Fraunhofer diffraction geometry), consists of a
periodic array of spots (sharp peaks of intensity) [1]. (Click here to know the conditions under which this is satisfied).
 From the real lattice the reciprocal lattice can be geometrically constructed. The properties
of the reciprocal lattice are ‘inverse’ of the real lattice → planes ‘far away’ in the real
crystal are closer to the origin in the reciprocal lattice.
 As a real crystal can be thought of as decoration of a lattice with motif; a reciprocal crystal
can be visualized as a Reciprocal Lattice decorated with a motif* of Intensities.
 Reciprocal Crystal = Reciprocal Lattice + Intensities as Motif*
 The reciprocal of the ‘reciprocal lattice’ is nothing but the real lattice!
 Planes in real lattice become points in reciprocal lattice and vice-versa.

 I.e. the information needed is the geometry of the lattice.

* Clearly, this is not the “crystal motif”- but a motif consisting of “Intensities”.
# The complete diffraction pattern (not the one observed in an experiment). The one observed in an experiment is a subset
of this, which can be found by the Ewald Sphere construction.
[1] The diffraction pattern can be obtained by Fourier transform of the crystal in real space.
A motivation for constructing reciprocal lattices
 In diffraction patterns (Fraunhofer geometry & under conditions listed here: (Click here to know the conditions under which this is
satisfied).) (e.g. SAD), planes are mapped as spots (ideally points). This as you will remember is the Bragg’s
viewpoint of diffraction. Hence, we would like to have a construction which maps planes in a real crystal
as points.
 Apart from the use in ‘diffraction studies’ we will see that it makes sense to use reciprocal lattice when
we are dealing with planes.
 The crystal ‘resides’ in Real Space, while the diffraction pattern ‘lives’ in Reciprocal Space.

 As the index of the plane increases

→ the interplanar spacing decreases
→ and ‘planes start to crowd’ in the real lattice (refer
figure).

 Hence, it is a ‘nice idea’ to work in reciprocal

space (i.e. work with the reciprocal lattice),
especially when dealing with planes.

As index of the plane increases, the

interplanar spacing decreases

In the figure the axes and origin are chosen locally

 We
Wewill
willconstruct
constructreciprocal
reciprocallattices
latticesinin1D
1Dand
and2D
2D
before taking up a formal definition in
before taking up a formal definition in 3D3D

Let us start with a one dimensional lattice and construct the reciprocal lattice

Real Lattice

Natura
l or igin of
th e recip
rocal la
ttice
O
Reciprocal Lattice

 The periodic array of points with lattice parameter ‘a’ is transformed to a reciprocal lattice
with periodicity of ‘1/a’.
 The reciprocal lattice point at a distance of 1/a from the origin (O), represents the whole set of
points (at a, 2a, 3a, 4a,….) in real space.
 The reciprocal lattice point at ‘2/a’ comes from a set of points with fractional lattice spacing
a/2 (i.e. with periodicity of a/2). The lattice with periodicity of ‘a’ is a subset of this lattice
with periodicity of a/2. (Refer next slide).
 The reciprocal lattice has a natural origin (labelled ‘O’). As we shall see it is indexed ‘0’.
w is this reciprocal lattice constructed?
 To construct the reciprocal lattice we need not ‘go outside’ the unit cell in real space! (We already
know that all the information we need about a crystal is present within the unit cell– in conjunction with translational symmetry).

 Just to get a ‘feel’ for the planes we will be dealing with in the construction of 3D reciprocal
lattices, we ‘extend’ these points perpendicular to the 1D line and treat them as ‘planes’.
Note there is only one “Miller” index in 1D
 The plane (2) has intercept at ½, plane (3) has intercept at 1/3 etc.
One unit cell
 As the index of the plane increases the interplanar spacing decreases
and the first in the setgets closer to the origin (there is overall
Real Lattice crowding).
 What do these planes with fractional indices mean?
 We have already noted the answer in the topic on Miller indices
and XRD.

Note: in 1D planes are points and have Miller indices of single digit (they have been extended into the
second dimension (as lines) for better visibility and for the reason stated above).

Each one of these points

correspond to a set of
‘planes’ in real space
Note that the indices in reciprocal
space have no brackets

0
Reciprocal Lattice
Note that in reciprocal space index
has NO brackets
Funda Check What do the various points (with indices 1, 2, 3, 4… etc.) represent in real space?
ce
‘1’ represents these set of planes in reciprocal space (with interplanar spacing ‘a’) a tti
lL
ca
p ro
ci
Re

Real Lattice
a

Real Lattice
Re

‘4’ represents these set of planes in reciprocal space (interplanar spacing a/4)
al
La
tti
ce

‘2’ represents these set of planes in reciprocal space (interplanar spacing a/2)

Zero represents the natural origin

of the reciprocal lattice 0

Reciprocal Lattice
‘1’ represents these set of planes in reciprocal space (interplanar spacing ‘a’)

tice
l Lat
Rea
‘3’ represents these set of planes in reciprocal space (interplanar spacing a/3)
Real Lattice

Note again: in 1D planes are points and have Miller indices of single digit (they have been extended into the second dimension (as lines) for better visibility and for the reason stated before).
w let us construct some 2D reciprocal lattices Square lattice
Example-1 Reciprocal Lattice

 The square lattice in 2D is defined by two basis vectors (a1 & a2).
 The planes in 2Dreal lattice become points in 2Dreciprocal lattice.
 E.g. the (10) plane in real space becomes the 10 point in reciprocal space.
 The
* basic vectors for the reciprocal lattice are
* defined by the (10) and (01) planes. I.e. the
b1 is the vector connecting 00 to 10 and the b2 is the vector connecting 00 to 01.
 Once we have the basis vectors, we can construct the entire reciprocal lattice.
Re Each one of these points correspond to a
al
La set of ‘planes’ in real space
tt
(01) ice Re
cip
ro
ca
l
02 12 22
La
tti
ce

1
 (11) a2
a2 (10)
01 11
(21) 21

a1
* g11* *
g 21 g vectors connect
b2 origin to reciprocal
lattice points

a1
* 10 20
The reciprocal lattice has a natural origin! 00 b1 1
a1
 If we overlay the real and reciprocal lattices then we can see that: 11 vector in reciprocal
space is orthogonal to the (11) planes in real space.
 I.e. planes in real space are orthogonal to the corresponding reciprocal lattice vector.
* * *
The 11 vector in reciprocal space is : g11  1  b1  1  b2
* * *
Any general vector in a 2D reciprocal lattice is given by: g hk  h b1  k b2
* * * *
This can be generalized to 3D as: g hkl  h b1  k b2  l b3

Note that the indices corresponding to the real spaces planes; i.e. h, k & l are retained as
subscripts to the vector g in the reciprocal space.

Note that vectors in reciprocal

Overlay of real and space are perpendicular to planes
reciprocal lattices
in real space (as constructed!)
But do not measure distances from the figure!
 Oblique lattice (parallogram)
Example-2 Re
cip
ro
ca
lL
att
ice


Re
al
a2
La
tt ic
e *
 b2
a1 *
b1
The reciprocal lattice

Note that vectors in reciprocal space

are perpendicular to planes in real
space (as constructed!)
But do not measure distances from the figure!
 Reciprocal Lattice (3D)
Properties are reciprocal to the crystal lattice
 To get the reciprocal lattice in 3D, we need 3 basis vectors.
 These are defined using the basis vectors of the crystal as below, where V is the volume of the
unit cell.
 The magnitude of the reciprocal lattice basis vector is (1/corresponding interplanar spacing).
* 1   * 1   * 1   * *
BASIS b  a a  2 b   a3  a1  b3   a1  a 2  bi is often written as ai
VECTORS 1 V 2 3 V V
* 1   Area (OAMB ) 1
b  b3   a1  a2  
*
3  
V Area(OAMB )  Height of Cell OP a3
1 b* is  to a and a *
b 
*
3 3 1 2 b3
d 001
C
P 
a2

BB
M

O A 
a1
The reciprocal lattice is created by interplanar spacings
Some properties of the reciprocal lattice and its relation to the real lattice
 A reciprocal lattice vector is  to the corresponding * * * *
real lattice plane g hkl  h b1  k b2  l b3
 The length of a reciprocal lattice vector is the reciprocal * 1
of the spacing of the corresponding real lattice plane g *
hkl  g hkl 
d hkl
 Planes in the crystal become lattice points in the reciprocal lattice
 Note that this is an alternate geometrical construction of the real lattice.
 Reciprocal lattice point represents the orientation and spacing of a set of planes.

Notation for basis vectors

  
Basis vectors in real space a 1 a2 a3 Lattice translation vectors (UC basis vectors)
*  *  * Reciprocal Lattice translation
Basis vectors in reciprocal space (lattice) b1 b2 b3 vectors (UC basis vectors)
 *  *  * Reciprocal Crystal: basis vectors
Basis vectors in reciprocal space (crystal) c1 c2 c3 of UC. New
 notation
General vector in real space ruvw  ua1  va2  wa3 “May be” identical to the basis
vectors of the reciprocal lattice
* * * *
General vector in reciprocal space g hkl  h b1  k b2  l b3
 Going from the reciprocal lattice to diffraction spots in an experiment
 A Selected Area Diffraction (SAD) pattern in a TEM is similar to a section through the
reciprocal lattice (or more precisely the reciprocal crystal, wherein each reciprocal lattice
point has been decorated with a certain intensity).
 The reciprocal crystal has all the information about the atomic positions and the atomic
species (i.e. I have to look into both the positions of the points and the intensities decorating them) .
evision+
 Reciprocal lattice* is the reciprocal of a primitive lattice and is purely geometrical
 does not deal with the intensities decorating the points.
Physics comes in from the following:
 For non-primitive cells ( lattices with additional points) and for crystals having motifs
( crystal = lattice + motif) the Reciprocal lattice points have to be weighed in with the
corresponding scattering power (|Fhkl|2) (Where F is the structure factor).
 Some of the Reciprocal lattice points go missing (or may be scaled up or down in
intensity).
 Making of Reciprocal Crystal: Reciprocal lattice decorated with a motif of scattering
power (as intensities).
 The Ewald sphere construction further can select those points (regions of
reciprocal space), which can be observed in a diffraction experiment.
 The intensity actually observed in an experiment depends on the ‘detector set-up’.
* as considered here
 The journey from the real lattice to the diffraction pattern Crystal = Lattice + Motif

To summarize: Real Lattice Diffraction Pattern

Decoration of the lattice with motif
Position of the diffraction spots
Real Crystal  RECIPROCAL LATTICE

Purely Geometrical Construction Intensity of the diffraction spots

 MOTIF’ OF INTENSITIES
Reciprocal Lattice
Decoration of the reciprocal lattice with Intensities * In fact the Ewald sphere
Structure factor calculation construction selects
Reciprocal Crystal regions of the reciprocal
space (which contains the
Ewald Sphere construction
Bragg diffraction pattern
Selection of some spots/intensities from the crystal(s) and
from the reciprocal crystal* Diffraction Pattern** diffuse intensities
(between the Bragg peaks).
In crystals based on a particular lattice the intensities of
particular reflections are modified  they may even go missing ** The actual diffraction
y pattern observed in an
Position of the diffraction spots
e db Lattice
experiment depends on
in
te rm the ‘detector setup’.
Intensity of the diffraction spots d e Motif
Is
Making of a Reciprocal Crystal

 Construct the reciprocal lattice and decorate each lattice point with appropriate intensity.
 Use the real crystal (atomic positions & atomic scattering factor (‘f’)) to compute the intensity, which
will decorate each lattice point (using structure factor calculations).
 Choose a new unit cell in reciprocal space if required.
 Use this new unit cell to describe the reciprocal crystal
 Reciprocal crystal = Reciprocal lattice + Intensity as motif.
These points will become clearer when we consider examples.

Real Lattice
Decorate with motif
Take real lattice and construct
Real Crystal reciprocal lattice
Use motif to compute (a pure geometrical construct)
structure factor and hence
intensities to decorate Reciprocal Lattice
reciprocal lattice points

Reciprocal Crystal
Reciprocal crystal in 1D (& 2D)
 Let us consider a 1D lattice with lattice parameter ‘a’ (Fig.0, next slide). Patch of an infinite lattice shown.
The lattice points also correspond to the set of (1) planes.
 Let us decorate this lattice with point scatterers (i.e. we do not have to consider the
dimension of the scatteres) (Fig.1). The scattering factor (f) is shown as -functions at each
lattice point (y-axis). This is equivalent to the atomic scattering factor for atoms.
 The reciprocal lattice can be constructed from the real lattice (Fig.2). The x-axis has
dimensions of [1/distance] and lattice spacing is 1/a. The reciprocal lattice points have been
indexed as 1, 2, 3, etc., which correspond to (1) , (2), (3) ‘planes’ (actually points in 1D) in the real
space lattice.
 The reciprocal crystal is constructed from the reciprocal lattice by weighing the same with
intensities (i.e. structure factor). This is shown as -functions along the y-axis (Fig.3).

Continued…
1D
1D  Fig.0: the lattice. Basis vector a.
 Fig.1: 1D crystal (with ‘atoms’). The y-axis (with -functions) is used to depict the scattering power.
 Fig.2: The reciprocal lattice. Basis vector b*.
 Fig.3. The reciprocal ‘crystal’. The reciprocal lattice decorated with intensities (y-axis used for this).


(Fig.0) Lattice (real space) a

(Fig.1) Crystal (real space)

*
(Fig.2) Reciprocal Lattice b

I f2
(Fig.3) ‘Reciprocal Crystal’

Continued…
2D
2D (Fig.0) Lattice (real space) Square lattice

a2 U
C
a1

(Fig.1) Crystal (real space)

(Fig.2) Reciprocal Lattice  U

b2* C

b1*

The diameter of the circles

represent intensities (f 2)

‘Reciprocal Crystal’ (Fig.3) Calculation of the intensity

shown in a later slide
 Q&A How to calculate the intensities, which decorate the reciprocal lattice (say in 2D)?
 We have to perform structure factor calculations (click here: Structure Factor Calculations).
 For this we use the formula as below.
In 3D n n
  f j e    f j e
i[2 ( h xj  k yj  l zj )]
F hkl i j
 Meaning of the terms is explained in the slides
n
j 1 j 1
 on Structure Factor Calculations

n n
  f j e    f j e
i[2 ( h xj  k y j )]
In 2D F hkl i j
 There is only one ‘atom’ (scatterer) at (0,0)
n
j 1 j 1


For the square crystal

F1hkl  f ei[2 ( h 0 k 0)]   f

I f2 At each reciprocal lattice

point resides an intensity f2
Funda Check What do the circled points represent in real space?

 Each of the points in the reciprocal lattice, corresponds to a set of planes in real space.
 The farther the point in reciprocal space from the origin (designated as 00), the finer will be
the inter-planar spacing in real space.
( 22)

( 21)

( 11)
 Q&A Construct the reciprocal crystal for the real space ‘super’-crystal in Fig.1 (1D).
The equation for the structure factor in 1D can be written as: f1 and f2 are the atomic scattering factors of the atoms
at (0) and (½)
n n
 f j e j    f j e
i[2 ( h xj )]
i
  f1ei[2 ( h .0)]  f 2 ei[2 ( h . 2 )]  f1e0  f 2ei h
1
hkl
F n 
j 1 j 1

(h) even F  f1  f 2 F 2  ( f1  f 2 ) 2 Fundamental

reflections (h) odd F  f1  f 2 Superlattice
F 2  ( f1  f 2 ) 2 reflections


(Fig.0) Lattice (real space) a

(Fig.1)
Crystal (real space)

*
(Fig.2) Reciprocal Lattice b

The ‘strong’ peaks are referred to as fundamental reflections and the ‘weak’ peaks as superlattice reflections
Fundamental reflections Superlattice reflections
(Fig.3) ‘Reciprocal Crystal’
*
Note: the periodicity of the reciprocal c
lattice is ‘1/a’ (vector b*), while that of
the reciprocal crystal is ‘2/a’ (vector c*).
ad these slides in parallel  Read the slides on Structure Factor Calculations

SC Examples of 3D Reciprocal Lattices weighed in with scattering power (|F|2)

Selection rule: All (hkl) allowed

In ‘simple’ cubic crystals there are No missing reflections
Reciprocal Crystal = SC
+  SC lattice with Intensities as the motif at each ‘reciprocal’ lattice point.
Single sphere  The unit cell for the reciprocal lattice and the reciprocal crystal are the
motif same in this case.

Lattice = SC

1/a
a SC crystal
= 1/a
a
a 1/a

Weighing factor for each point “motif”

gures NOT to Scale F2  f 2
CCP Reciprocal Crystal = BCC
BCC lattice with Intensities as the motif
 Selection rule FCC: h, k, l unmixed (all odd or all
even).
 Allowed reflections: 111, 200, 220...
 Forbidden reflections: 100, 110, 112...
 BCC lattice with Intensities (16f2) as the motif at each
‘reciprocal’ lattice point.
a  The unit cell for the reciprocal lattice and the reciprocal
crystal are NOT the same in this case.
 The basis vectors for the UC of the reciprocal lattice:
(b1)*, (b2)*, (b3)*.
 The basis vectors for the UC of the reciprocal crystal:
(c1)*, (c2)*, (c3)*.
Important note:
 The 100, 110, 112, etc. points in the reciprocal lattice exist (as the
corresponding real lattice planes exist), however the intensity
decorating these points is zero.
100 missing
reflection (F = 0)

Weighing factor for each 110 missing reflection

point “motif” (F = 0)

F 2  16 f 2
Figures NOT to Scale
 Selection rule BCC: (h+k+l) even allowed Reciprocal Crystal = CCP
BCC In BCC 100, 111, 210, etc. go missing
FCC lattice with Intensities as the motif

100 missing
reflection (F = 0)

2/a
Weighing factor for
each point “motif”

F2  4 f 2

Figures NOT to Scale

Order-disorder transformation and its effect on diffraction pattern

 When a disordered structure becomes an ordered structure (at lower temperature), the
symmetry of the structure is lowered and certain superlattice spots appear in the Reciprocal
Lattice/crystal (and correspondingly in the appropriate diffraction patterns). Superlattice
spots are weaker in intensity than the spots in the disordered structure.
 An example of an order-disorder transformation is in the Cu-Zn system: the high temperature
structure can be referred to the BCC lattice and the low temperature structure to the SC
lattice (as shown next). Another examples are as below.
 The phenomenon is associated with diffuse scattering (presence of lower ‘diffuse’ intensity)
between the Braggs’ peaks. This is not considered here.

Disordered Ordered
- NiAl, BCC B2 (CsCl type)
- Ni3Al, FCC L12 (AuCu3-I type)
Click here to know more about Superlattices & Sublattices Click here to know more about Ordered Structures
 Diagrams not to scale

Positional Order In a strict sense this is not a crystal !!

High T disordered

BCC

Probabilistic occupation of each BCC lattice site:

50% by Cu, 50% by Zn
G = H  TS 470ºC

Sublattice-1 (SL-1)

Sublattice-2 (SL-2)

Low T ordered SC

SL-1 occupied by Cu and SL-2 occupied by Zn. Origin of SL-2 at (½, ½, ½)

 Disordered Ordered Click here to see structure factor
calculation for NiAl (to see why
- NiAl, BCC B2 (CsCl type) some spots have weak intensity)
→ Slide 27

Click here to see XRD powder

pattern of NiAl → Slide 5

Ordered

FCC
BCC SC

or the ordered structure:

Reciprocal Crystal = ‘FCC’

FCC lattice with Intensities as the motif

Notes: Reciprocal crystal

 For the disordered structure (BCC) the reciprocal crystal is FCC.
 For the ordered structure the reciprocal crystal is still FCC but with
a two intensity motif: ‘Strong’ reflection at (0,0,0) and superlattice
(weak) reflection at (½,0,0) .
 So we cannot ‘blindly’ say that if lattice is SC then reciprocal
lattice is also SC.

This is like the NaCl structure

in Reciprocal Space!
 Disordered Ordered Click here to see structure factor
calculation for Ni3Al (to see
- Ni3Al, FCC L12 (AuCu3-I type) why some spots have weak
intensity) → Slide 29

Click here to see XRD powder

pattern of Ni3Al → Slide 6

Ordered

BCC
FCC
SC

Reciprocal Crystal = BCC

BCC lattice with Intensities as the motif

Reciprocal crystal
 Sorry for so many repetitions often the term ‘reciprocal lattice’
Q&A How to construct the reciprocal and structure factor calculation can strike a discordant note!
crystal?
 Using the geometry of the unit cell of the lattice in the real space, construct the reciprocal lattice.
 Perform structure factor calculations to compute the intensities which decorate each reciprocal lattice
point. We have noted that some of the intensities may even be zero (the missing reflections) and some of
the intensities may be weak in the case of superlattices (& ordered structures) the superlattice
reflections.
 This gives rise to a reciprocal crystal. The reciprocal crystal may have a different unit cell as compared to
the reciprocal lattice. This unit cell (new/old), with basis vectors (new/old) can be used to define the
reciprocal crystal.
 This reciprocal crystal can now be defined using the standard language
 Reciprocal Crystal = (new/old) Reciprocal Lattice + Intensities as Motif.

Lattice = BCC
Motif = 1FR (0,0,0) + 3SLR {(½,0,0), (0,½,0), (0,0,½)}

 FR  Fundamental Reflection
 SLR  Superlattice Reflection

Lattice = FCC
Motif = 1FR (0,0,0) + 1SLR (½,0,0)
Example of superlattice spots in a TEM diffraction pattern

The spots are

~periodically arranged

[112]
[111] [011]
Superlattice spots

SAD patterns from a BCC phase (a = 10.7 Å) in as-cast Mg4Zn94Y2 alloy showing important zones
Example of superlattice peaks in XRD pattern

NiAl pattern from 0-160 (2)

Superlattice reflections (weak)

The Ewald Sphere* Paul Peter Ewald (German physicist and crystallographer; 1888-1985)
 The reciprocal crystal is a map of the crystal in reciprocal space → but it does not tell us
which spots/reflections would be observed in an actual experiment.
 The Ewald sphere construction selects those points/regions of reciprocal space, which can
be observed in a diffraction experiment.
 The intensities which may be actually observed in a diffraction experiments depends on the
‘detection system’.

Circular of a Colloquium held at Max-Planck-Institut

für Metallforschung (in honour of Prof.Ewald) 7. Paul-Peter-Ewald-Kolloquium
Freitag, 17. Juli 2008

13:30 Joachim Spatz (Max-Planck-Institut für Metallforschung)

Begrüßung

13:45 Heribert Knorr (Ministerium für Wissenschaft, Forschung und Kunst Baden-Württemberg
Begrüßung organisiert von:
Max-Planck-Institut für Metallforschung
14:00 Stefan Hell (Max-Planck-Institut für Biophysikalische Chemie)
Nano-Auflösung mit fokussiertem Licht Institut für Theoretische und Angewandte Physik,
14:30 Antoni Tomsia (Lawrence Berkeley National Laboratory)
Institut für Metallkunde,
Using Ice to Mimic Nacre: From Structural Materials to Artificial Bone Institut für Nichtmetallische Anorganische Materialien
15:00 Pause der Universität Stuttgart
Kaffee und Getränke Programmt
15:30 Frank Gießelmann(Universität Stuttgart)
Von ferroelektrischen Fluiden zu geordneten Dispersionen von Nanoröhren: Aktuelle Themen der Flüssigkristallforschung

16:00 Verleihung des Günter-Petzow-Preises 2008

16:15 Udo Welzel (Max-Planck-Institut für Metallforschung)

Materialien unter Spannung: Ursachen, Messung und Auswirkungen- Freund und Feind

ab 17:00 Sommerfest des Max-Planck-Instituts für Metallforschung

The Reciprocal Lattice & the Ewald Sphere Readers may refer to Cullity’s book (A15-4) for a nice
account of the same.
 The reciprocal lattice points are the values of momentum transfer for which the Bragg’s
equation is satisfied.
 For diffraction to occur the scattering vector must be equal to a reciprocal lattice vector.
 Geometrically  if the origin of reciprocal space is placed at the tip of ki then diffraction
will occur only for those reciprocal lattice points that lie on the surface of the Ewald sphere.
 Here, for illustration, we consider a 2D section thought the Ewald Sphere (the ‘Ewald
Circle’). Construction of the Ewald sphere is considered next.
Bragg’s equation revisited

n   2 d hkl Sin hkl This is Bragg’s equation in

reciprocal space
Rewrite  2 1 d hkl
Sin hkl  
d hkl 2
 Draw a circle with diameter 2/
 Construct a triangle with the diameter as the
hypotenuse and 1/dhkl as a side: AOP
(any triangle inscribed in a circle with the
diameter as the hypotenuse is a right angle
triangle: APO = 90):
 The angle opposite the 1/d side is hkl (from the
rewritten Bragg’s equation)
 Now if we overlay ‘real space’ information on the Ewald Sphere. (i.e. we are going to ‘mix-
up’ real and reciprocal space information).
 Assume the incident ray along AC and the diffracted ray along CP. Then automatically the
crystal will have to be considered to be located at C with an orientation such that the d hkl
planes bisect the angle OCP (OCP = 2).
 OP becomes the reciprocal space vector ghkl (often reciprocal space vectors are written without the ‘*’).

* 1
g *
hkl  g hkl 
d hkl
The Ewald Sphere construction Which leads to spheres for various hkl reflections
Crystal related information is present in the reciprocal crystal

 2 1 d hkl
Sin hkl   The Ewald sphere construction generates the diffraction pattern
d hkl 2
Chooses part of the reciprocal crystal which is observed in an experiment

Radiation related information is present in the Ewald Sphere

 When the Ewald Sphere (shown as circle in 2D

Reciprocal Space below) touches the reciprocal lattice point 
that reflection is observed in an experiment (41
reflection in the figure below).
 It is clear that the circle was drawn (w.r.t the
lattice) in such a way that it passes through 41.
In general such an intersection is not
2q guaranteed.
KD
Ki
02
The Ewald Sphere touches the
01 reciprocal lattice (for point 41)
DK (41)
 Bragg’s equation is satisfied for 41
00 10 20
41
K = K =g = Diffraction Vector
Ewald sphere  X-rays Diffraction from Al using Cu K radiation

Row of
Rows of reciprocal
reciprocal lattice
lattice points
points

The 111 reflection is observed at a

smaller angle 111 as compared to the
222 reflection

(Cu K) = 1.54 Å, 1/ = 0.65 Å−1 (2/ = 1.3 Å−1), aAl = 4.05 Å, d111 = 2.34 Å, 1/d111 = 0.43 Å−1
Ewald sphere  X-rays
Now consider Ewald sphere construction for two different
crystals of the same phase in a polycrystal/powder (considered
next).

Click
Clicktotocompare
comparethem
them

(Cu K) = 1.54 Å, 1/ = 0.65 Å−1 (2/ = 1.3 Å−1), aAl = 4.05 Å, d111 = 2.34 Å, 1/d111 = 0.43 Å−1
Funda Check
In the example considered previously, the Ewald circle passes through the 41 reciprocal
lattice/crystal point (Fig.1). Such an intersection is very rare. Then how do we observe
so many reflections in XRD and TEM?
 To increase the chance of obtaining a reflection, we can use some
Reciprocal Space
methods.
a) Use a powder sample, wherein crystallites are in all random
orientations and hence each reciprocal lattice point becomes a circle
Fig.1 (in 2D) centred around the origin 00. This will ensure the existence
2q
Ki
KD of a reflection (proviso Sin <1). This is referred to as the powder diffraction
02 method.
01 b) Rotate the crystal during XRD. This is called the rotating crystal
DK (41)

00 10 20
method.

c) Use panchromatic radiation (i.e. X-rays with a range of wavelengths). In this case the Ewald sphere
will have a range of radii and hence intersection with the reciprocal mutiple lattice points is
possible.
d) Use short wavelength radiation along with a thin sample (like in a TEM). This makes the Ewald
circle flat and each of the reciprocal lattice spots becomes a rel rod. This will help sample many
reciprocal lattice points on a single reciprocal lattice plane. Fig.2. More about how this happens in the chapter on
TEM diffraction.

Fig.2
Not to scale !
THE POWDER METHOD Diffraction cones and the Diffractometer geometry

 In the powder method we use monochromatic radiation (  is fixed), but  is variable (the
sample consists of crystallites in various orientations).
 A cone of ‘diffraction beams’ are produced from each set of planes (e.g. (111), (120) etc.)
(As to how these cones arise is shown in an upcoming slide). A vertical mid-section through the cones
shown in the figure below.
 A diffractometer is typically used in modern XRD studies, which moves in an arc and can
intersect these cones and give rise to peaks in a ‘powder diffraction pattern’.

The intersection of th path of the

diffractometer with the cones of
diffracted intensity.

Click here for more details regarding the powder method

‘3D’ view of the ‘diffraction cones’ THE POWDER METHOD

Different cones for different reflections

Diffractometer moves in a semi-circle to capture the intensity of the diffracted

Understanding the formation of the cones

 Let us consider two planes (say with indices {111}) the
green plane and the blue plane. These are residing in two
different crystals and are perfectly oriented at Bragg angle for
diffraction.
 These two set of planes result in the blue and green diffracted
beams.
 Similar planes (again from the {111} family as an illustration)
from other crystallites in the specimen can be obtained by
using the axis of rotation (red font). This forms a cone of
diffracted beams.
 THE POWDER METHOD

 In a powder sample, due to ‘all’ orientations of the crystallites the point ‘P’ ‘expands’ a
circle with centre at ‘O’.
 The intersection of the Ewald sphere with the ‘crystal sphere’ is a circle and this gives rise
to the cone of intensity.

Cone of diffracted rays

Circle of intersection of the ‘Ewald

sphere’ with the crystallites sphere

In a power sample the point P can

lie on a sphere centered around O
due all possible orientations of the
crystals
The distance PO = 1/dhkl
 Circular Section through the spheres
made by the hkl reflections

The 440 reflection is not observed

(as the Ewald sphere does not intersect
the reciprocal lattice point sphere)

Ewald sphere construction for Al

Allowed reflections are those for
h, k and l unmixed
 The 331 reflection is not observed

Ewald sphere construction for Cu

Allowed reflections are those for
h, k and l unmixed
End
 There are two ways of constructing the Reciprocal Crystal:
Construct the lattice and decorate each lattice point with appropriate intensity
Use the concept as that for the real crystal (lattice + Motif)

) SC + two kinds of Intensities decorating the lattice

) (FCC) + (Motif = 1FR + 1SLR)

Motif
 FR  Fundamental Reflection NiAl
 SLR  Superlattice Reflection

) SC + two kinds of Intensities decorating the lattice

) (BCC) + (Motif = 1FR + 3SLR)
Ni3Al

Motif
 The above two approaches are equivalent for simple crystals (SC, BCC, FCC lattices
decorated with monoatomic motifs), but for ordered crystals the two approaches are
different (E.g. ordered CuZn, Ordered Ni3Al etc.) (as shown soon).

* Point #1 has been considered to be consistent with literature– though this might be inappropriate.
** Point #2 makes reciprocal crystals equivalent in definition to real crystals