Crystallography and X-Ray Diffraction

MM323

Fall 2019

Course Instructor: Dr. Muhammad Imran Khan (PhD,

Tsukuba University, Japan)

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 Credit hours: 3
Prerequisites: MM102
Text and Reference Books:
 The Basic Principles of Crystallography and Diffraction by CRISTOPHER HAMMOND (3 rd
ed. 2009) *
 Elements of X-Ray Diffraction by B.D. CULLITY (3rd ed. 2001) *
 X-ray Diffraction and Crystallography by Yoshio Waseda (2011)
 Essentials of Crystallography by D. McKie (1986)
 Basic Elements of Crystallography by Nevill Gonzalez Szwacki & Teresa Szwacka
(2010)

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 Course Evaluation

Final Term Exam: 40%

Mid Term Exam: 30%

Quizzes: 15%

Assignments: 5%

Course Project/presentations: 10%

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 Contact Details

Office : G 05
Phone: 2543

[email protected]
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 Course Syllabus
Crystallography:

Introduction to crystals and crystal systems, Construction of crystals and packing of

layers, Interstitial structures, tetrahedral and octahedral sites in HCP, BCC and FCC,,
Crystal projections, Stacking faults and twins , Two-dimensional patterns, lattices and
symmetry , Bravais lattices and crystal systems, Plane group symmetry, Crystal
symmetry, Crystal symmetry and properties, Point group symmetry, space groups, Quasi-
crystals. Zone axis, Zone law, Miller indices, Reciprocal lattices.
.

X-Ray Diffraction:

Introduction to X-rays, Safety precautions, diffraction, Lau’s approach for X-ray

diffraction, Bragg’s analysis of X-ray diffraction, Diffraction methods (Powder method,
Laue technique, Crystal rotating method), Ewald’s sphere construction, Structure factor
calculations, Indexing patterns , X-ray diffraction of polycrystalline materials, texture
analysis, Lattice parameter measurements , Identification of unknown phases,
Measurement of crystal (grain) size, Measurement of internal elastic strains, Crystal
structure determination, Hanawalt method, Quantitative analysis, Amorphous and
crystalline nature and XRD patterns, Application of XRD, Electron diffraction and its
applications, The stereographic projection and its uses. .
5
 Lecture – 1,2,3

 Course Objectives
 Introduction to Crystals and Crystal Structures

 Nature of crystalline state

 Crystals from hexagonal close pack layers of atoms
 Unit Cells of hexagonal close pack structures (hcp) and
 cubic close pack structures (ccp)
 Crystals from square layer of atoms
 Constructing Body centered cubic crystal
 Interstitial structures
 Simple Ionic and covalent structures
 Crystal Planes
 Stacking faults and Twins
--
6
 Objectives of this course:

 To develop basic concepts of crystal structures of

materials

 To know basic principles of crystallography , symmetry,

points groups etc

 Structures determination

 Phase analysis and Phase diagrams determination

 Residual stresses measurements

7
 Nature of Crystalline State

External Evidences of having internal Order/Pattern

“Lack of external
crystalline form lack
of internal regularity”
DO YOU AGREE??

Cleavage Fracture
surfaces of brittle
Fe

snowflakes
Faceted minerals shape

Various attempts were made to uncover the mystery behind the external patterns
i.e INTERNAL ORDER of ATOMS
X-rays or Electron Diffraction => most materials are crystalline/partly..
8
Robert Hooke suggested that the
different shapes of crystals which
occur—rhombs, trapezia,
hexagons, etc.—could arise from
the packing together of spheres or
globules.

Scheme VII’(from Hooke’s Micrographia, 1665),

showing crystals in a piece of broken flint
1912, Lau diagrams
by Lau
Internal order

external symmetry

Williams Laurence
Bragg

Law of reflection of
X-rays (Bragg Law)
Structural Analysis of
Crystals

10
 Hard sphere Model of Atoms- 2D structures

Hexagonal Arrays square arrays

Close packing: which Case? Voids/gaps Interstices

11
 Constructing crystals from close pack
hexagonal layers of atoms
Simple hexagonal
structres
AAAA…
A=1st layer
Hexagonal Close B=2nd layer
pack (hcp) C=3rd layer
structures
ABABAB….
Stacking sequence of close packed layer of atoms
Zn, Mg, Low temp.
form of Ti

• A is the first layer (with the circular outlines of the atoms drawn in) and
• B is the second layer (outlines of the atoms not shown for clarity).
• In the first case the third layer goes directly above the A layer, the fourth
layer over the B layer, and so on; the stacking sequence then becomes
ABABAB…and is called the hexagonal close-packed (hcp) structure.
13
There are, in fact, no
examples of elements with
this structure
• The packing of idealized hard spheres predicts
a ratio of interlayer atomic spacing to in-layer
atomic spacing of √(2/3)
• *(Exercise 1.1)
• Although interatomic forces cause deviations
from this ratio, metals such as zinc,
magnesium and the low-temperature form of
titanium have the hcp structure.
 Constructing crystals from close pack
hexagonal layers of atoms
Combination of
Cubic close pack hcp and ccp :
structures (ccp)
ABACABAC….
Stacking sequence Examples;
ABCABC…. Actinides,
lanthanides
Cu, Al, Au, high temp. Stacking Faults:
form of Fe ABAB..+ ABCABC..
ccphcp
Three layer stacking of hexagonal layers of atoms is cubic close packed
structure. why? Shape and Symmetry

• In the second case, the third layer of atoms goes above the
interstices marked C and the sequence only repeats at the fourth
layer, which goes directly above the first layer.

• The stacking sequence is now ABCABC…and is called the

cubic close-packed (ccp) structure. 17
Unit Cells of hcp and ccp structures
Simple hexagonal

ccp
In ccp, the close-packed layers lie perpendicular to the
body diagonal of the cube, but as there are four
different body diagonal directions in a cube, there are
hcp therefore four different sets of close-packed layers.
18
 Crystals from square layer of Atoms

Simple cubic
(it is an uncommon
structure. An
example of an
Four close
element with
packed layers a simple cubic
structure is α-
polonium. )

ccp structure 19
 Constructing bcc structures

Stacking
sequence:
ABABAB…

Transformations from bcc to ccp or hcp and vise versa may occur
Example: Fe quenching/cooling from high temp. to low temperature

Cr, Mo, High temp. form of Ti and low temp. form

of Fe
20
Unit Cells of hcp and ccp structures

Rhombohedral unit cell

No cubic symmetry

21
• The different structures of very many compounds arise from the different
numbers and sizes of interstices which occur in the simple hexagonal, hcp,
ccp, simple cubic and bcc structures

• Also from the ways in which the small atoms or cations distribute
themselves among these interstices.

• In the ccp structure there are two types and sizes of interstice into which
small atoms or cations may fit.
• Tetrahedral interstice or tetrahedral interstitial site.
• Octahedral interstice or octahedral interstitial site.
• The diameters, or radii, of atoms or ions which can just fit into these
interstices may easily be calculated on the basis that atoms or ions are
spheres of fixed diameter— the ‘hard sphere’ model.

• The results are usually expressed as a radius ratio, rX/rA; the ratio of the
radius (or diameter) of the interstitial atoms, X, to that of the large atoms,
A, with which they are in contact.
 Interstitial Structures
Tetrahedral Sites

rX/rA = 0.225

Octahedral Sites

rX/rA = 0.414

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Tetrahedral and octahedral sites in ccp
Tetrahedral case Octahedral case: plan
view

rX/rA = 0.225 rX/rA = 0.414

25
Cubic interstitial site

rX/rA = 0.732

Caesium chloride, CsC1, has this structure

26
Octahedral and tetrahedral sites in bcc

Radius ratio =
0.154

Radius ratio =
0.291

27
 Assignment-1
1. For both the octahedral sites in ccp, and the cubic sites in
the simple cubic structure, the proportion is one interstitial
site to one (large) atom or ion. How?

2. For the tetrahedral interstitial sites in ccp the proportion is

two sites to one atom. How?

Submit the assignment in hand written form within 2

days.
 29

X-RAY
• X-rays were discovered in 1895
by the German physicist Wilhelm
Conrad Röntgen and were so
named because their nature was
unknown at the time.

• He was awarded the Nobel prize

for physics in 1901.

Wilhelm Conrad Röntgen

(1845-1923)
A bit of History
• William Roentgen discovered X-rays in
1895 and determined they had the
following properties
1. Travel in straight lines
2. Are exponentially absorbed in matter
with the exponent proportional to the
mass of the absorbing material
3. Darken photographic plates
4. Make shadows of absorbing material
on photosensitive paper
• Roentgen was awarded the Nobel
Prize in 1901
• Debate over the wave vs. particle
nature of X-rays led the development
of relativity and quantum mechanics
 31

X-RAY PROPERTIES
• X ray, invisible, highly penetrating electromagnetic radiation of
much shorter wavelength (higher frequency) than visible light.
The wavelength range for X rays is from about 10-8 m to about 10-
11
m, the corresponding frequency range is from about 3 × 1016 Hz
to about 3 × 1019 Hz.
The Electromagnetic Spectrum
Cu-Kα
 Discovery of Diffraction
• Max von Laue theorized that if X-rays
were waves, the wavelengths must be
extremely small (on the order of 10-10
meters)
• If true, the regular structure of
crystalline materials should be
“viewable” using X-rays
• His experiment used an X-ray source
 The image created showed: directed into a lead box containing an
1. The lattice of the crystal oriented crystal with a photographic
produced a series of regular
spots from concentration of the x-
plate behind the box
ray intensity as it passed through
the crystal and Von Laue’s results were
2. Demonstrated the wave published in 1912
character of the x-rays
3. Proved that x-rays could be
diffracted by crystalline materials
 Bragg’s “Extensions” of Diffraction
• Lawrence Bragg and his father W.H. Bragg discovered that
diffraction could be treated as reflection from evenly spaced
planes if monochromatic x-radiation was used.

• Bragg’s Law: n = 2d sin

• where n is an integer

•  is the wavelength of the X-radiation

d is the interplanar spacing in the crystalline material
and  is the diffraction angle

• The Bragg Law makes X-ray powder diffraction possible

 Notes on Units of Measure
• an angstrom (Å) is 10-10 meters
• a nanometer (nm) is 10-9 meters
• a micrometer (m) or micron is 10-6 meters
• a millimeter (mm) is 10-3 meters

In X-ray crystallography, d-spacings and X-

ray wavelengths are commonly given in
angstroms
 36

X-RAY ENERGY
• Electromagnetic radiation described as having
packets of energy, or photons. The energy of the
photon is related to its frequency by the following
formula:
E  h
c
E
hc  
 

hc
 =Wavelength , ‫ = ע‬Frequency , c = Velocity of light E 


 ≈ 10 -10
≈ 1A° E ~ 104 ev
x-ray
 Generating X-rays for Diffraction
 To get an accurate picture of the structure of a crystalline
material requires X-radiation that is as close to
monochromatic as possible.

 The function of the x-ray tube and associated electronics is

to produce a limited frequency range of high-intensity x-
rays.

 Filters, monochromators, specially tuned detectors and

software are then used to further refine the frequency used
in the analysis.
 The X-ray Tube
• Schematic cross section of an X-ray
tube

• The anode is a pure metal. Cu, Mo, Fe,

Co and Cr are in common use in XRD
applications. Cu is used on our Scintag
system

• The tube is cooled by water and

housed in a shielding aluminum tower
 39

PRODUCTION OF X-RAYS
• X-rays are produced by the movement of
electrons in atoms. Electrons occupy different
energy levels, or orbitals, around an atom's
nucleus.

• When an electron drops to a lower orbital, it needs

to release some energy; it releases the extra energy
in the form of a photon. The energy level of the
photon depends on how far the electron dropped
between orbitals.
X-rays Tube Schematic
 Characteristics of Common Anode Materials
Materia At. # K1 K2 (Å) Char Opt Advantages (Disadvantages)
l (Å) Min kV
(keV)
Cr 24 2.290 2.294 5.98 40 High resolution for large d-spacings,
particularly organics (High
attenuation in air)
Fe 26 1.936 1.940 7.10 40 Most useful for Fe-rich materials
where Fe fluorescence is a problem
(Strongly fluoresces Cr in
specimens)
Co 27 1.789 1.793 7.71 40 Useful for Fe-rich materials where
Fe fluorescence is a problem
Cu 29 1.541 1.544 8.86 45 Best overall for most inorganic
materials (Fluoresces Fe and Co K
and these elements in specimens can
be problematic)
Mo 42 0.709 0.714 20.00 80 Short wavelength good for small
unit cells, particularly metal alloys
(Poor resolution of large d-spacings;
optimal kV exceeds capabilities of
most HV power supplies.)
 Generation of X-rays
c • X-rays may be described as waves and
 (1) particles, having both wavelength () and
energy (E)
 • In the equations at left:

E  h (2)
–
–
–
E is the energy of the electron flux in KeV
h is Planck’s constant (4.135 x 10-15 eVs)
v is the frequency
– c is the speed of light (3 x 1018 Å/s)
hc –  is the wavelength in Å

E (3)
 • Substituting (1) into (2) yields (3), the
relationship between wavelength and energy.

12.398 • In (4) all constants are substituted

E (4)

 Continuous Spectrum
• X-rays are produced whenever matter is irradiated with a beam
of high-energy charged particles or photons

• In an x-ray tube, the interactions are between the electrons and

the target. Since energy must be conserved, the energy loss
from the interaction results in the release of x-ray photons

• The energy (wavelength) will be equal to the energy loss

(Equation 4).

• This process generates a broad band of continuous radiation

(a.k.a. bremsstrahlung or white radiation)
 44

Continuous X-ray Spectra

The continuous spectra consists of a range of wavelengths of X-rays with minimum
wavelength and intensity (measured in counts per second) dependent on the target
material and the voltage across the X-ray tube.  The minimum wavelength decreases
and the intensity increases as voltage increases.
Continuous Spectrum
hc 12.398
 min  
V V

• The minimum wavelength ( in

angstroms) is dependent on the
accelerating potential ( in KV) of
the electrons, by the equation
above.

• The continuum reaches a

maximum intensity at a
wavelength of about 1.5 to 2
times the min as indicated by the
shape of the curve
 46

Characteristic X-ray Spectra

• When the voltage of the X-

ray Tube is raised above
certain critical value, sharp
intensity maxima appear at
certain wavelengths.
 47

Generation of X-rays
Continuous and Characteristic
Spectrum
Characteristic Wavelength values (in Å)
for Common Anode Materials
Anode K1 (100) K2 (50) K (15)

Cu 1.54060 1.54439 1.39222

Cr 2.28970 2.29361 2.08487

Fe 1.93604 1.93998 1.75661

Co 1.78897 1.79285 1.62079

Mo 0.70930 0.71359 0.63229

* Relative intensities are shown in parentheses

 50

X-RAY TUBE
 X rays can be produced in a highly evacuated glass bulb, called
an X-ray tube, that contains essentially two electrodes—an
anode made of platinum, tungsten, or another heavy metal of
high melting point, and a cathode. When a high voltage is
applied between the electrodes, streams of electrons (cathode
rays) are accelerated from the cathode to the anode and
produce X rays as they strike the anode.

Evacuated glass bulb

Cathode
Anode
 51

DIFFRACTION
• Diffraction is a wave phenomenon in
which the apparent bending and spreading
of waves when they meet an obstruction.

• Diffraction occurs with electromagnetic

waves, such as light and radio waves, and
also in sound waves and water waves. Width b Variable
(500-1500 nm)
Wavelength Constant
(600 nm)
• The most conceptually simple example of
Distance d = Constant
diffraction is double-slit diffraction, that’s
why firstly we remember light diffraction.
 52

LIGHT DIFFRACTION
• Light diffraction is caused by light bending around the edge of an
object.
• The interference pattern of bright and dark lines from the
diffraction experiment can only be explained by the additive
nature of waves; wave peaks can add together to make a brighter
light, or a peak and a trough will cancel each other out and result
in darkness.

Thus Young’s light interference

experiment proves that light
has wavelike properties.
 53

Constructive & Destructive

Waves
• Constructive interference is • Destructive İnterference .
the result of synchronized results when two out-of-
light waves that add phase light waves cancel each
together to increase the light other out, resulting in
intensity. darkness.
 54

Light Interference
• The diffraction of light is most easily demonstrated
using a laser.

• Many everyday objects may be used as ‘diffraction

gratings’ either in transmission or reflection.

• fabrics, nets, (transmission) or graduated metal rulers

(reflection) and the resultant diffraction patterns may
be projected on to a wall or screen.
 57

Diffraction from a particle and solid

Single particle
• To understand diffraction we also have
to consider what happens when a wave
interacts with a single particle. The
particle scatters the incident beam
uniformly in all directions

Solid material
• What happens if the beam is incident
on solid material? If we consider a
crystalline material, the scattered
beams may add together in a few
directions and reinforce each other to
give diffracted beams
 58

Diffraction of Waves by Crystals

A crystal is a periodic structure
( unit cells are repeated regularly)

Solid State Physics deals how the waves are propagated through
such periodic structures. Here we study the crystal structure through
the diffraction of X-rays.

X-ray Diffraction Electron Diffraction Neutron Diffraction

The general princibles will be the same for each type of waves.
Roadmap
• In the simple cubic structure there is one
interstice (cubic site) per unit cell
• In ccp there are four octahedral sites per cell.
• In ccp there are eight tetrahedral sites per unit
cell.
 Simple Hexagonal structure: Interstitial site

Radius Ratio = rX/rA = 0.527

Radius ratio

By the help of radius ratio of interstitial

sites, interpretation of some important
compounds become easy.
BUT this ratio still have some problems as
State of coordinatio
atomic radius do not remains same ionization n
Example
atomic radius of Li = 156pm  atomic radius of Li+ = 60pm 61
Atomic radius, Fe (ccp), = 258pm  atomic radius, Fe(bcc),=248pm
Coordination Number and radius ratio

62
 Coordination numbers
CN in Simple Cube (SC) unit Cell CN in body centered cube (bcc)
6 unit Cell  8

63
 Example:
 The radius of Na +1 = 1.02 Å,
 The radius of Cs = 1.67 Å,
+1
 Radius of Cl-1 = 1.81 Å
 Radius of Cl-1 = 1.81 Å  radius ratio = 0.56
 radius ratio = 0.92
See Table (previous slide)
See Table (previous slide)

64
• In the bcc structure there are octahedral sites at the centers of
the faces and mid-points of the edges and tetrahedral sites
situated between the centers of the faces and mid-points of
each edge .
• In the simple hexagonal structure the interstitial sites are
coordinated by six atoms—three in the layer below and three
in the layer above .

• It is the same coordination as for the octahedral interstitial

sites in the ccp structure except that in this case the
surrounding six atoms lie at the corners of a prism with a
triangular base, rather than an octahedron, and the radius ratio
is, rX/rA = 0.527
• The radius ratios of interstitial sites and their
proportions provide a very rough guide in
interpreting the crystal structures of some simple,
but important, compounds.

• The problem is that the ‘radius’ of an atom is not a

fixed quantity but depends on:

1. Its state of ionization (i.e. upon the nature of the chemical

bonding in a compound)
2. Coordination (the number and type of the surrounding
atoms or ions).
• Metal hydrides, nitrides, borides, carbides, etc., in which the
radius ratio of the (small) non-metallic or metalloid atoms to
the (large) metal atoms is small, provide good examples of
interstitial compounds.

• In almost all of these compounds the interstitial atoms are

‘oversize’ (in terms of the exact radius ratios) and so, in effect,
‘push apart’ or separate the surrounding atoms such that they
are no longer strictly close-packed although their pattern or
distribution remains unchanged.
TiN structure TiH2 structure TiH structure

NaCl structure CaF2 structure Diamond

ZnS structure
structure

70
• Consider the structure of TiN; the nitrogen atoms occupy all
the octahedral interstitial sites and, because they are oversize,
the titanium atoms are separated but still remain situated at the
corners and face centers of the unit cell.
•
• This is described as a face-centered cubic (fcc) array, rather
than a ccp array of titanium atoms, and TiN is described as a
face-centered cubic structure.

• This description also applies to all compounds in which some

of the atoms occur at the corners and face centers of the unit
cell.
• The ccp structure may be regarded as a special
case of the fcc structure in which the atoms are
in contact along the face diagonals.
• bcc metals such as vanadium, tungsten or iron (low
temperature form) form interstitial compounds in which the
metal atoms are arranged in an fcc pattern (e.g. VC), a simple
hexagonal pattern (e.g. WC) or more complicated patterns
(e.g. Fe3C).

• No elements have the simple hexagonal structure in which the

close-packed layers are stacked in an AAA…sequence directly
on top of one another

• The metal atoms in some metal carbides, nitrides, borides,

etc., are stacked in this way, the carbon, nitrogen, boron, etc.,
atoms being situated in some or all of the interstices between
the metal atoms.
• Although there are no bcc interstitial compounds as such,
interstitial elements can enter into the interstitial sites in the
bcc structure to a limited extent to form what are known as
interstitial solid solutions.

• One very important example in metallurgy is that of carbon in

the distorted octahedral interstitial sites in iron, a structure
called ferrite.
• The radius ratio of carbon to iron, rC/rFe, is about 0.6, and the
solubility of carbon is very small—1 carbon atom in about 200
iron atoms.

• The carbon atoms ‘push apart’ the two closest iron atoms and
distort the bcc structure in a non-uniform or a uniaxial way—
and it is this uniaxial distortion which is ultimately the origin
of the hardness of steel.
• In contrast, a much greater amount of carbon can enter the
(uniform) octahedral interstitial sites in the ccp (high
temperature) form of iron (called austenite)—1 carbon atom in
about 10 iron atoms.

• The carbon atoms are still oversize, but the distortion is a

uniform expansion and the hardening effect is much less.
 Stacking Faults and Twins
• ‘Nature makes mistakes’ and may do so in a number of ways.

• First, stacking faults may occur during crystallization from the

melt or magma

• Second, they may occur during the solid state processes or

recrystallization, phase transitions and crystal growth (i.e.
during the heating and cooling of metalsand alloys, ceramics
and rocks).

• Third, they may occur during deformation.

Stacking Faults and Twins
Stacking Faults and Twins
Stacking Faults and Twins
• Faults are of considerable importance in
metallurgy because of the effects of faulting on
the mechanical and thermal properties of
alloys:

– Strength,
– Work-hardening,
– Softening temperatures etc.
ABCABCABC......
ABCBABC....?
ABCBCABC...?Any Difference?

ABCBABC.... It is as if the mis-stacked B layer had been inserted into the

ABCABC…sequence and this is called an extrinsic stacking fault

ABCBCABC... it is as if an A layer had been removed from the ABCABC…sequence,

and this is called an intrinsic stacking fault.
• In practice we need to invoke some parameter which provides
a measure of the occurrence of stacking faults and twins.

• This is provided by the concept of the stacking fault energy

(units mJ m−2):
– It is simply the increased energy (per unit area) above that
of the normal (unfaulted) stacking sequence.

• The lower the stacking fault energy, the greater the occurrence
of stacking faults.
• The energy of a twin boundary is about half that of an intrinsic
stacking fault.

• The energy of an extrinsic stacking fault is about double that

of an intrinsic stacking fault.

• Stacking faults, and the concept of stacking fault energy, play

a very important role in the deformation of metals.

• During deformation—rolling, extrusion, forging and so on—

the regular, crystalline arrangement of atoms is not destroyed.
• Metals do not, as was once supposed, become amorphous.

• The deformation is accomplished by the gliding or sliding of

close-packed layers over each other.

• The overall gliding directions are those in which the rows of

atoms are close-packed

• But, as will also be evident from the models, the layers glide
in a zig-zag path, from ‘hollow to hollow’ and passing across
the ‘saddle-points’ between them.
• The B layer may stop at a C position (partial slip), in which case
we have an (intrinsic) stacking fault.

• This partial slip is represented by the arrows or vectors B→C or

C→B.
• Extrinsic stacking faults, twins and the ccp → hcp transformation
may be accomplished by mechanisms involving the partial slip of
close-packed layers.
 Two-dimensional patterns, lattices
and symmetry
• Important concepts of symmetry, motifs and lattices.

R, an asymmetric shape

R, the repeating ‘unit of pattern’ is called the motif.

 Two-dimensional patterns, lattices
and symmetry
• These motifs may be considered to be situated at or near the
intersections of an (imaginary) grid.

• The grid is called the lattice and the intersections are called
lattice points.
If we know:

(1) The size and shape of the unit cell.

(2) The motif which each lattice point represents, including its
orientation with respect to the lattice point.

• We can draw the whole pattern or build up the whole structure

indefinitely.
• The unit cell of the lattice and the motif therefore define the
whole pattern or structure.
• Each motif is identical.

• For an infinitely extended pattern, the environment

(i.e. the spatial distribution of the surrounding motifs,
and their orientation) around each motif is identical.

• A lattice:
– A lattice is an array of points in space in which the
environment of each point is identical.
Regular Arrays or lattices. Are they same????
• Figure (a) and (d) represent two two-dimensional lattice types, named oblique
and rectangular, respectively, in view of the shapes of their unit cells.

• What is the distinction between the oblique and rectangular lattices?

Two-dimensional patterns, lattices
and symmetry

R M S
• The ten arrangements of Rs (and the corresponding two-
dimensional motifs or projections of molecules) are called the
ten two-dimensional crystallographic or plane point
groups.

• Because all the symmetry elements—axes (perpendicular to

the page) and mirror lines (in the page)—pass through a point.
• The ten plane point groups are labelled with ‘shorthand’
symbols.

• 1 for a monad (no symmetry)

• m for one mirror line,
• mm (or 2mm) for two mirror lines (plus diad), 2 for a diad
• 3 for a triad, 3m for a triad plus three mirror lines,
• 4 for a tetrad, 4mmfor a tetrad plus four mirror lines,
• 6 for a hexad and 6mmfor a hexad plus six mirror lines
 Crystallographic restriction theorem
• The crystallographic restriction theorem in
its basic form was based on the observation
that the rotational symmetries of a crystal are
usually limited to 2-fold, 3-fold, 4-fold, and 6-
fold.

• Quasicrystals can occur with other diffraction

pattern symmetries, such as 5-fold; these were
not discovered until 1982 by Dan Shechtman.
• In deriving the ten plane point groups the groups of Rs with
fivefold (pentad), seven-fold (heptad) etc. axes of symmetry
with and without mirror lines have been ignored. ????
• Such plane point groups are certainly possible and are widely
represented in nature.

• The pentagonal symmetry of a starfish for example.

• what makes the ten plane point groups special or distinctive is

that only these combinations of axes and mirror lines can
occur in regular repeating patterns in two dimensions.

• Hence they are properly called the two-dimensional

crystallographic point groups.
• Patterns with pentagonal symmetry are necessarily non-
repeating, non-periodic or and consequently have in the past
been rather overlooked by crystallographers.

• With the realization that groups of atoms (or viruses) can form
‘quasicrystals’ with five-fold symmetry elements the study of
non-periodic two-dimensional patterns has become of
increasing interest and importance
• A quasi-periodic crystal, or quasicrystal, is a structure that is
ordered but not periodic.

• The quasicrystals are no longer a unique form of solid

• they exist universally in many metallic alloys and some

polymers.

• Quasicrystals are found most often in aluminium alloys (Al-

Li-Cu, Al-Mn-Si, Al-Ni-Co, Al-Pd-Mn, Al-Cu-Fe, Al-Cu-V,
etc.)

• But numerous other compositions are also known (Cd-Yb, Ti-

Zr-Ni, Zn-Mg-Ho, Zn-Mg-Sc, In-Ag-Yb, Pd-U-Si, etc.)
 The five plane lattices
• Having examined the symmetries which a two-dimensional
motif may possess it can now be determined how many two-
dimensional or plane lattices there are..

• This can be done by building up patterns from the ten motifs.

• The important condition is that the symmetry elements

possessed by the single motif must also extend throughout the
whole pattern.
• Consider the asymmetrical motif R:

• There are no symmetry elements to be considered and the R

may be repeated in a pattern with an oblique unit cell
• Now consider the motif which possesses one ‘vertical’ mirror
line of symmetry.
• This mirror symmetry must extend throughout the whole pattern from motif to
motif which means that the lattice must be rectangular.

There are two possible arrangements of lattice points which fulfill this requirement:
a simple rectangular lattice and a centered rectangular lattice.

These rectangular lattices also possess ‘horizontal’ mirror lines of symmetry

corresponding to the motif with the two sets of mirror lines.
• Now consider the motifs with tetrad (four-fold) symmetry.

• This fourfold symmetry must extend to the surrounding motifs

which means that they must be arranged in a square pattern
giving rise to a square lattice.
• Altogether, five two-dimensional or plane lattices may be
worked out.
• All two-dimensional patterns must be based upon one
of these five plane lattices; no others are possible.

• This may seem very surprising—surely other shapes

of unit cells are possible?

• The answer is ‘yes’, a large number of unit cell

shapes are possible, but the pattern of lattice points
which they describe will always be one of the five
 Asignment#2
• Chapter # 1
– Exercise #1.1, 1.2, 1.3, 1.5, 1.6, 1.8

– Hand written
– Due date: Tuesday 22 sep 2019
• For example, the rectangular c lattice may also be described as
a rhombic p or diamond p lattice, depending upon which unit
cell is chosen to ‘join up’ the lattice points

The rectangular c lattice, showing the alternative primitive (rhombic p or diamond

p) unit cell.

These are just two alternative descriptions of the same

arrangement of lattice points.
• So the choice of unit cell is arbitrary: any four lattice points
which outline a parallelogram can be joined up to form a unit
cell.

• In practice we take a sensible course and mostly choose a unit

cell that is as small as possible—or ‘primitive’ (symbol p)—
which does not contain other lattice points within it.

• Sometimes a larger cell is more useful because the axes

joining up the sides are at 90◦.
• Examples are the rhombic or diamond lattice which is
identical to the rectangular centred lattice and,

• To take an important three-dimensional case, the cubic cell

which is used to describe the ccp structure in preference to the
primitive rhombohedral cell

ccp in the ‘ABC …’ sequence but the

resulting rhombohedral cell
• There are ten point group symmetries which a motif
can possess.

• It may be thought that there are therefore only ten

different types of two-dimensional patterns.

• There is a complication:

– The combination of a point group symmetry with a lattice

can give rise to an additional symmetry element called a
glide line.
Notice that in (b) one set of Rs has been translated, or glided half a lattice spacing.

This symmetry is called a reflection glide or simply a glide line of symmetry.

Glide lines also arise automatically in the centre of the unit cell of as do mirror lines.
• Glide lines are, of course, as familiar to us as mirror lines;
they represent the pattern of our footprints in the snow when
we walk in a straight line.

• The presence of the glide lines also has important

consequences regarding the symmetry of the motif.

In Fig. (a) the motif has mirror symmetry but in Fig.(b) it

does not: the pair of right- and left-handed Rs is asymmetric.
• It is the repetition of the translational
symmetry elements—the glide lines—that
determines the overall rectangular symmetry
of the pattern.
 The seventeen plane groups
• Glide lines give seven more two-dimensional patterns, giving
seventeen in all—the seventeen plane groups.

• On a macroscopic scale the glide symmetry in a crystal would

appear as simple mirror symmetry.

• The shift between the mirror-related parts of the motif would

only by observable in an electron microscope which was able
to resolve the individual mirror-related parts of the motif, i.e.
distances of the order of 0.5–2 Å (50–200 pm).
• It is essential to practice recognizing the
motifs, symmetry elements and lattice types
in two-dimensional patterns and therefore to
find to which of the seventeen plane groups
they belong.
The molecules or groups of atoms are not identical in this two-dimensional
projection.

The motif is a pair of such molecules and this is the ‘unit of pattern’ that is
repeated.

The lattice is clearly oblique and the plane group is p2.

• It is essential to practice recognizing the motifs,
symmetry elements and lattice types in two-
dimensional patterns and therefore to find to which of
the seventeen plane groups they belong.
 One-dimensional symmetry: border or
frieze patterns
• In plane patterns the symmetry operations and symmetry
elements are (clearly) repeated in a plane.

• In one-dimensional patterns they can only be repeated in or

along a line—i.e. the line or long direction of the border or
frieze.

• This restriction immediately rules out all rotational symmetry

elements with the exception of diads.
 One-dimensional symmetry: border or
frieze patterns
• For the same reason glide-reflection lines of symmetry, other
than that along the line of the border, are ruled out.

• Mirror lines of symmetry are restricted to those along, and

perpendicular to, the line of the border.

• These restrictions result in seven one-dimensional groups.

 Symmetry in art and design:
counterchange patterns
• A rich inheritance of plane and border patterns in printed and
woven textiles, wallpapers, bricks and tiles.

• Have all the seventeen plane groups and seven one-

dimensional groups been utilized in pattern design or are some
patterns and some symmetries more evident than others?

• The study of plane and one-dimensional patterns (and indeed

three-dimensional (space) patterns) is complicated by the
question of colour.
• Clearly, the greater the number of colors, the greater the complexity.
• The simplest cases to consider are two-colour (e.g. black and white) patterns.
• Counterchange or colour symmetry elements
• Altogether there are eleven counterchange point groups
Accounting for two-colour symmetry gives rise to a total of forty-six
(rather than seventeen) plane patterns and seventeen (rather than
seven) one-dimensional patterns.
 Bravais lattices and crystal systems

• The definitions of the:

– Motif, the repeating ‘unit of pattern.

– The lattice, an array of points in space in which each point

has an identical environment.

• hold in three dimensions exactly as they do in two dimensions.

• In three dimensions there are additional
symmetry elements that need to be
considered:
 Point group symmetries of 3D motifs and the resulting translational symmetries of
the crystal (motif + Lattice)  increase group symmetries

Symmetry elements in 2D crystals Symmetry elements in 3D crystals

Mirror lines Mirror planes

Glide lines Glide planes

Rotational axis Rotational axis

Inversion axis

Screw axis

2D crystals 3D crystals

10 plane point group symmetry 32 point group symmetry

5 plane lattices 14 space lattices

17 plane groups 230 space groups

Bravais Lattices
• Cubic I and cubic F with primitive rhombohedral unit cell
• Inter-axial angle is shown;

• BUT these primitive unit cells are not used rather I and F cubic
is preferred. Because of two reasons
– Interaxial angle is not convenient
– Cubic symmetry is not clearly revealed.

143
• The rhombohedral and cubic lattices are related.

• The primitive cells of the cubic I and cubic F lattices

are rhombohedral.

• The axes are of equal length and the angles (α)

between them are equal.

• As in the two-dimensional cases, what distinguishes

the cubic lattices from the rhombohedral is their
symmetry.
• When the angle α is 90◦ we have a cubic P lattice,

• When it is 60◦ we have a cubic F lattice

• When it is 109.47◦ we have a cubic I lattice

• Or, alternatively, when the hexagonal layers of lattice

points in the rhombohedral lattice are spaced apart in
such a way that the angle α is 90◦, 60◦ or 109.47◦,
then cubic symmetry results.
• The Bravais lattices may be thought of as
being built up by stacking ‘layers’ of the
five plane lattices, one on top of another.
 Plane lattices Versus Bravais Lattices

Stacking of plane lattices on top of each other  Bravais lattices

1. Square lattices  cubic and tetragonal

2. Rectangular lattices  Orthorhombic P and I lattices
3. Centered rectangular orthorhombic C and F Lattices
4. Hexagonal lattices  rhombohedral and hexagonal lattices
5. Oblique lattices  monoclinic and triclininc lattices

Hexagonal lattice
AAAA… rhombohedral lattice
ABCABC..…
Cubic Versus Rhombohedral :

Distinction is based on their

symmetry
147
 Comparison of orhtorhombic versus tetragonal lattices

 Why there is no C and F tetragonal lattices as compared to orthorhombic where P,

I, C and F lattices possible?

Tetragonal P = C lattices tetragonal I = F lattices

148
 The symmetry of the fourteen Bravais
lattices: crystal systems
• Mirror lines of symmetry become mirror planes in three
dimensions.

• Axes of symmetry (diads, triads, tetrads and hexads) also

apply to three dimensions.

• The additional complication is that, whereas a plane motif or

object can only have one such axis (perpendicular to its
plane).

• A three-dimensional object can have several axes running in

different directions (but always through a point in the centre
of the object).
• The cubic unit cell contains a total of nine mirror planes, three parallel to
the cube faces and six parallel to the face diagonals.

• There are three tetrad (four-fold) axes perpendicular to the three sets of
cube faces.

• Four triad (three-fold) axes running between opposite cube corners.

• Six diad (two-fold) axes running between the centres of opposite edges.

• This ‘collection’ of symmetry elements is called the point group

symmetry of the cube because all the elements—planes and axes—pass
through a point in the centre.
• The cubic unit cell has more symmetry elements than any
other: its very simplicity makes its symmetry difficult to grasp.

• More easy to follow is the symmetry of an orthorhombic cell.

• It contains, like the cube, three mirror planes parallel to the

faces of the cell.

• The only axes of symmetry are three diads perpendicular to

the three faces of the unit cell.
• In both cases it can be seen that the point group symmetry of
these unit cells is independent of whether the cells are centred
or not.

• All three cubic lattices, P, I and F, have the same point group
symmetry; all four orthorhombic lattices, P, I , F and C, have
the same point group symmetry and so on.

• This simple observation leads to an important conclusion: it is

not possible, from the observed symmetry of a crystal, to tell
whether the underlying Bravais lattice is centred or not.
• Therefore, in terms of their point group symmetries,
the Bravais lattices are grouped, according to the
shapes of their unit cells, into seven crystal systems.

• For example, crystals with cubic P, I or F lattices

belong to the cubic system, crystals with
orthorhombic P, I , F or C lattices belong to the
orthorhombic system, and so on.
• A complication arises in the case of crystals with a hexagonal
lattice.

• One might expect that all crystals with a hexagonal lattice

should belong to the hexagonal system, but, the external
symmetry of crystals may not be identical (and usually is not
identical) to the symmetry of the underlying Bravais lattice.
 XX
• Some crystals with a hexagonal lattice, e.g. α-quartz, do not
show hexagonal (hexad) symmetry but have triad symmetry.
• Such crystals are assigned to the trigonal
system rather than to the hexagonal system.

• Hence the trigonal system includes crystals

with both hexagonal and rhombohedral
Bravais lattices.
 Crystal Systems and Symmetry

Crystal System Minimum Symmetry elements

Cubic Four 3-fold rotation axis
Tetragonal One 4-fold rotation
Orthorhombic Three 2 fold rotation
Trigonal One 3-fold rotation
Hexagonal One 6-fold rotation
Monoclinic One 2-fold rotation
Triclinic None
 Ordering the 7 Crystal Systems: Symmetry

Order
Cubic Cubic

Hexagonal Hexagonal
Tetragonal
Increasing symmetry

Tetragonal
Trigonal
Trigonal
Orthorhombic
Orthorhombic
Monoclinic
Monoclinic

Triclinic Triclinic

Arrow marks lead from supergroups to subgroups

 The coordination or environments of Bravais
lattice points: space-filling polyhedra

• Lattices as patterns of points in space in which each lattice

point has the same environment in the same orientation.

• This approach is complete and sufficient, but it fails to

stress, or even make clear, the fact that:

– Each of these environments is distinct and characteristic of

the lattices themselves.

– We need therefore a method of clearly and unambiguously

defining what we mean by ‘the environment’ of a lattice
point.
The coordination or environments of Bravais
lattice points: space-filling polyhedra

• One approach is to state this in terms of

‘coordination.

– For example, in the simple cubic (cubic P) lattice

each lattice point is surrounded by six other
equidistant lattice points.

– In the bcc (cubic I ) lattice each lattice point is

surrounded by eight equidistant lattice points
• An alternative and much more fruitful approach is to
consider the environment or domain of each lattice
point in terms of a polyhedron.

• Whose faces, edges and vertices are equidistant

between each lattice point and its nearest neighbours.
• In geometry, a polyhedron is simply a three-
dimensional solid which consists of a
collection of polygons, usually joined at their
edges.
The edges of the polyhedron are where the faces intersect and represent points
which are equidistant between the central lattice point and two other surrounding
lattice points.

The vertices of the polyhedron represent points which are equidistant between the
central lattice point and three other surrounding points.
• However, for lattices of higher symmetry this correspondence
does not hold.

• If, for example, we consider a cubic P lattice, square in plan,

and follow the procedure outlined, we find that the polyhedron
is (as expected) a cube.

• The edges of which are equidistant between the central lattice

point and three surrounding lattice points and the vertices of
which are equidistant between the central lattice point and
seven surrounding lattice points.
• The polyhedra constructed in this way and which represent the
domains around each lattice point have various names:
Dirichlet regions or Wigner-Seitz cells or Voronoi∗ polyhedra.

• There are altogether 24 such space-filling polyhedra

corresponding to the 14 Bravais lattices;

• it is not a simple one-to-one correspondence in all cases

because the shape of the polyhedron may depend upon the
ratios between the axial lengths and angles and whether the
Bravais lattice is centred or not.
 Symmetry and crystal habit
Sugar cube unit
cell stacking

Common symmetry : Four 3-fold rotation axis

167
 Symmetry and crystal habit
Point Group
Symmetery

• Issues;
• As Crystallographers, how crystals can be put
in specific crystal systems?
Or
• How one can identify the crystal system of a
crystal with entirely different shape as
compared to its unit cell?

168
 Symmetry and crystal habit
Sugar cube unit
cell stacking

Common symmetry : Four 3-fold rotation axis

169
 Symmetry and crystal habit
• The cube and octahedron, although they are different shapes,
possess the same point group symmetry.

• The tetrahedron, however, has less symmetry:

– only six mirror planes instead of nine: only three diads running
between opposite edges (i.e. along the directions perpendicular to the
cube faces in the underlying cubes) and, as before, four triads running
through each corner.

• The common, unchanged symmetry elements are the four

(equally inclined) triads.

• it is the presence of these four triads which characterizes

crystals belonging to the cubic system.
 Symmetry and crystal habit
• Cubic crystals usually possess additional symmetry
elements.

• the most symmetrical cubic crystals being those with

the full point group symmetry of the underlying unit
cell.

• But it is the four triads—not the three tetrads or the

nine mirror planes—which are the ‘hallmark’ of a
cubic crystal.
 Symmetry and crystal habit
Similar considerations apply to all the other crystal systems.

Figure (a) shows a crystal with the full symmetry of the underlying unit cell—three
perpendicular mirror planes and three perpendicular diads.

Figure (b) shows a crystal with only two mirror planes and one diad along their line
of intersection.

Figure (c) shows a crystal with three perpendicular diads but no mirror planes. 172
 Symmetry and crystal habit
• The examples shown in Figs 4.1–4.3 are of crystals with
different point group symmetries: they are said to belong to
different crystal classes.

• Crystals in the same class have the same point group

symmetry, so in effect the terms are synonymous.

• Notice that crystals in the same class do not necessarily have

the same shape.

• For example, the cube and octahedron are obviously different

shapes but belong to the same class because their point group
symmetry is the same.
• In two dimensions we found that there were ten plane point
groups; in three dimensions there are thirty-two three-
dimensional point groups.

• The concept of seven different types or shapes of underlying

unit cells then links up with the concept of the fourteen
Bravais lattices.

• In other words, it establishes the connection between the

external crystalline form or shape and the internal molecular
or atomic arrangements.
 The shape of the crystal will ‘reflect’ the point group symmetry
of the crystal

Crystals having same point group symmetry will belong the

same crystal system

Concept of Bravais Concept of 7 Crystal

Lattices Systems

32 Crystal classes/
Nomenclature rather than systematic
3D point Groups study of each group, focus on additional
symmetry elements

Problem Statement: Crystals usually do not crystallizes into regular

size or shapes (equal sides, same shapes of facets etc.)

Law of Constancy of Interfacial Angle: Interfacial angles of the crystal of a particular substance
is always constant in spite of different shapes and sizes and mode of growth of crystal. (also
called as Steno's Law)
175
 32 POINT
GROUP
SYMMETRY

176
 Center and Inversion Axis of Symmetry

Think about the

Center of crystal in this i ??
Symmetry way!!!!!!!!

Center of Symmetry Versus Mirror Plane of Symmetry

180o rotation

177
• If a crystal, or indeed any object, possesses a centre of
symmetry, then any line passing through the centre of the
crystal connects equivalent faces, or atoms, or molecules.

• The important relationship between these two symmetry

elements:
– A centre of symmetry plus a rotation of 180◦ (of one hand) is
equivalent to a mirror plane of symmetry.

• Conversely, a mirror plane of symmetry plus a rotation of 180◦

(about an axis perpendicular to the mirror plane) is equivalent
to a centre of symmetry.
• In short, centers and mirror planes of symmetry relate
objects which (like hands) do not themselves possess
these symmetry elements;

• Conversely objects which themselves possess these

symmetry elements do not occur in either right or
left-handed forms
• In two dimensions a centre of symmetry is
equivalent to diad symmetry.

• In three dimensions this is not the case

• Inversion axes of symmetry are rather difficult to
describe without the use of the stereographic
projection:

– A method of representing a three-dimensional pattern of

planes in a crystal on a two-dimensional plan.

• Inversion axes are compound symmetry elements,

consisting of a rotation followed by an inversion.
Example of Stereographic Projections
Crystal Symmetry and Properties

183
 Crystal Symmetry and Properties
• The quantities which are used to describe the properties of
materials are, as we know, simply represented as
coefficients, i.e. as one measured (or measurable) quantity
divided by another.

– For example, the property (coefficient) of electrical conductivity is

given by the amount of electrical current flowing between two points
(which may be measured in various ways) divided by the electrical
potential gradient.

– The pyroelectric effect—the property of certain crystals of developing

electrical polarization when the temperature is changed—is given by
the polarization divided by the temperature change.

– The heat capacity is given by the quantity of heat absorbed or given out
divided by the temperature change, and so on.
• In many (in fact most) cases the measured
quantities depend on direction and are called
vectors.

• Electrical current flow, potential gradient and

polarization are all vectors.

• Temperature change, quantity of heat, do not

depend on direction and are called scalars.
• The important point is that, in those cases where one
or more of the measured quantities vary with
direction, so also do the crystal properties.

• They are said to be anisotropic

• Anisotropy clearly arises because the arrangements of

atoms in crystals vary in different directions

• Anisotropy clearly arises because the arrangements of

atoms in crystals vary in different directions
• One would intuitively expect crystals to be
anisotropic

• One would also intuitively expect cubic crystals to be

‘less anisotropic’ than, say, monoclinic ones because
of their greater symmetry

• For many properties, but not all, cubic crystals are

isotropic
• Cubic crystals are isotropic with respect to
electrical conductivity.

• They are also isotropic with regard to the

pyroelectic effect, i.e. cubic crystals do not
exhibit electrical polarization when the
temperature is changed;

• The pyroelectic coefficient is zero.

• But cubic crystals are not isotropic with respect to all
properties.

• For example, their elastic properties, which determine

the mechanical properties of stiffness, shear and bulk
moduli, are direction dependent

• these are very important factors with respect to the

properties of metals and alloys.
 Zone Axis
• A zone may be defined as ‘a set of faces or
planes in a crystal whose intersections are all
parallel’.

• The common direction of the intersections is

called the zone axis.
 Generating Characteristic Radiation
• The photoelectric effect is
responsible for generation of
characteristic x-rays. Qualitatively
here’s what is happening:

– An incoming high-energy
photoelectron disloges a k-shell
electron in the target, leaving a
vacancy in the shell

L-shell to K-shell jump – An outer shell electron then

produces a K x-ray “jumps” to fill the vacancy
M-shell to K-shell jump
produces a K x-ray – A characteristic x-ray (equivalent
to the energy change in the
“jump”) is generated
• The photoelectric effect is the observation
that many metals emit electrons when light
shines upon them. Electrons emitted in this
manner can be called photoelectrons. The
phenomenon is commonly studied in
electronic physics, as well as in fields of
chemistry, such as quantum chemistry or
electrochemistry.
Crystals representation in Projections: crystal
Plans

bcc plan view fcc plan view ZnS plan view 197
Crystals representation in Projections: crystal Plans

198
 Why crystal projections used??
GROUP ASSIGNMENT-01
 Draw the crystal projections of following unit cells
 Do they belong to same type of structures ?
• ABX3 type structure ( e.g CaTiO3 )

SAME Structures
or NOT??????

Yes, They are of same structures (perovskite) because the

origin selection is at different atoms/ions ONLY
200