Presented to: Prof. Dr.

Mehmet Ali Glgn

SYMMETRY &
SPACE GROUPS

Presented by:
Muhammad Faisal Jamil
Yelda Yorulmaz
Amin Hodaei
MAT-509
Sabanci University
04 December, 2015

A TIMELINE OF SYMMETRY IN PHYSICS,

CHEMISTRY AND MATHEMATICS
1890s, derivation of the 230 space groups in 3 dimensions (independently) by Arthur Moritz Schnflies, Evgraf
Stepanovich Federov, and William Barlow
1936, Frederick Seitz works out the representation theory of space groups, the symmetry groups of crystal lattices.

A. M. Schnflies

E. S. Federov

W. Barlow

F. Seitz

SYMMETRY AND CRYSTALS

Think, if you
have to describe an infinite crystal with an infinite number of atoms or
even a finite crystal, with some 1020 atoms.
Sounds awful?
Well, there is symmetry to help you out!
Instead of an infinite number of atoms, you only need to describe the contents of one
unit cell, the structural repeating motif
Life could be even easier, if there are symmetry elements present inside the unit cell!

BASIC TERMINOLOGIES
Atomic structures repeating itself in 3D is termed as Translational Symmetry
Structures consist of simple groups of atoms that repeat periodically in space. This
periodicity is called Lattice.

Crystal structure of the mineral cordierite (Mg 2Al4Si5O18)

Source: http://www.doitpoms.ac.uk/tlplib/crystallography3/intro.php

BASIC TERMINOLOGIES
Set of identical points is the lattice, and each point within it is a lattice point.

Source: http://www.doitpoms.ac.uk/tlplib/crystallography3/lattice.php

BASIC TERMINOLOGIES
Structure of a crystal can be seen to be composed of a repeated element in 3D, called Unit Cell. There
are two types:
Primitive Unit Cell: These cells have only one lattice point, which is made up from the lattice points
at each of the corners.
Non-Primitive Unit Cell: These contain additional lattice points, either on a face of the unit cell or
within the unit cell, and so have more than one lattice point per unit cell.

Source: http://www.doitpoms.ac.uk/tlplib/crystallography3/unit_cell.php

LATTICE SYMMETRY
Lattice symmetry refers to unit cells size and shape.
Without rules, there would be an infinite number of different unit cells to describe any given
lattice.

Source:
http://www.aps.anl.gov/Xray_Science_Division/Powder_Diffraction_Crystallography/Introduction_to_Crystallography/#03

LATTICE GEOMETRY

The length of the unit cell along the x, y, and z direction are defined as a, b, and c. Alternatively, we can think of the
sides of the unit cell in terms of vectors a, b, and c. The angles between the crystallographic axes are defined by:

= the angle between b and c

= the angle between a and c
= the angle between a and b
a, b, c, , , are collectively known as the lattice parameters or unit cell parameters or cell parameters.
Source: http://www.doitpoms.ac.uk/tlplib/crystallography3/parameters.php

LATTICE VECTORS
A lattice vector is a vector joining any two lattice points. Any lattice vector can be written as a linear combination of
the unit cell vectors a, b, and c:
t = Ua + Vb + Wc
In shorthand, lattice vectors are written in the form:
t = [UVW]
Negative values are not prefixed with a minus sign. Instead a bar is placed above the number to denote that the value
is negative:
t = Ua + Vb Wc
This lattice vector would be written in the form:
t = [V]

Source: http://www.doitpoms.ac.uk/tlplib/crystallography3/parameters.php

COMMON TYPES OF UNIT CELLS

Source: http://www.doitpoms.ac.uk/tlplib/crystallography3/unit_cell.php

CRYSTAL STRUCTURE
The structure of a crystal can be described by using the lattice type, the lattice parameters, and the motif.
Lattice Type: Defines the location of the lattice points within the unit cell.
Lattice Parameters: Defines the size and shape of the unit cell.
Motif: List of the atoms associated with each lattice point, along with their fractional coordinates relative to the
lattice point.
For example, for ZnS
Crystal structure:

Cubic

Lattice type: Face centered

Motif:

Zn @ (0, 0, 0)
S @ (, , )

Source: http://www.doitpoms.ac.uk/tlplib/crystallography3/parameters.php

7 CRYSTAL SYSTEMS

Source: http://chemistrytextbookcrawl.blogspot.com.tr/2012/08/chapter-3.html

Source: http://202.141.40.218/wiki/images/JK-table1.png

14 BRAVAIS LATTICES

Source: http://learn.crystallography.org.uk/learn-crystallography/what-is-a-crystal/

SYMMETRY AND
SYMMETRY ELEMENTS
Symmetry: In crystallization, the search for a minimum free energy and the regular
packing of molecules, the crystal lattice often leads to a symmetric relationship between
the molecules in addition to the unit cell translations in the crystal lattice.
Rotation
axis
Point
Symmetry

Mirror
planes
Rotationinversion
centers

Symmetry
Elements

Screw axis
Translation
Symmetry
Glide planes

POINT SYMMETRYROTATION AXIS

Symbol: n (e.g., 2, 3, 4, 6)
An n-fold rotation axis will rotate
the object by 360/n
2-fold: Diad; 3-fold: Triad; 4fold: Tetrad; 6-fold: Hexad
No change in handedness referred to as proper symmetry
operation
The only rotational symmetries
possible in a crystal lattice are 2,
3, 4 and 6, because it is not
possible to fill space with other
symmetries.

POINT SYMMETRYMIRROR PLANES

Symbol: m
A mirror plane changes the
handedness of the object it is
operating on.
Cannot exist in crystals of
an enantiomerically pure
substance.
Referred to as improper
symmetry operation.

POINT SYMMETRYINVERSION CENTERS

Symbol: i
Turning an object inside
out
Equivalent to a point
reflection through the
inversion center.
Similar to focal point of a
lens.
Changes handedness

TRANSLATIONAL SYMMETRYSCREW AXIS

Translation of an object by half a unit cell in

the direction of the screw axis + 180 rotation.
E.g.,
2-fold screw 21
x, y, z = -x, -y, z + 1/2

TRANSLATIONAL SYMMETRYGLIDE PLANES

Reflection and translation: a, b, c, n or d.

Reflection across plane + translation of (usually) 1/2 a
unit cell parallel to plane along a, b, c, face diagonal
(n), or body diagonal (d)

SPACE GROUPS
Space groups are combination of point and translational symmetry operators.
Translational symmetry operations yield
14 Bravais Lattices (3D)
Point symmetry operations yield
32 Point Groups (3D)
Combining simple point and translation symmetry elements together yields
73 Space Groups
Two additional symmetry operations are possible
Glides translation plus reflection by a mirror
Screws translation plus rotation
Combining these two operations yields 157 additional space groups
Final total is 230 possible ways to repeat a motif in 3D or 230 Space Groups

SPACE GROUPS
How to read (and understand) Volume A of
International Tables for Crystallography: an
introduction for nonspecialists
Z. Dauter et al.,
J. Appl. Cryst. (2010). 43, 11501171

Symmetry Properties and Their

Relations to Electrical Properties
Point groups as a factor for electrical properties
Number of rotational axes and reflection planes
Lack of center of symmetry

What is the center of symmetry?

Point which crystal structure displays inversion symmetry.
Ex: Benzene

Fig: Benzene is a centrosymmetric molecule having a center of symmetry at the center

https://en.wikipedia.org/wiki/Centrosymmetry#/media/File:Centrosymmetr

Symmetry Properties and Their

Relations to Electrical Properties
Dielectric Polarization and Polar Materials
All materials form dipoles when there is an applied E
Some of them has already dipoles without the effect
of E

How do we decide if a material is polar or not?

By looking its crystal structure
If it is symmetric anti-polar
If it has lack of center of symmetry Polar

Fig: Dielectric
polarization

http://hyperphysics.phy-

32 Crystallographic Point
Groups
21 Noncentrosymmetric

11
Centrosymmetric

20
Piezoelectric
10
Pyroelectric
Ferroelectr
ic

1 Nonpiezoelectric

10 Nonpyroelectric

Nonferroelectric

 Ex: BaTiO3
Above Tc=120C Cubic structure
Centrosymmetric
No spontaneous dipole moment
Dielectric (Anti-polar)

Below Tc=120C Tetragonal structure

Lack of center of symmetry
Creates dipole moment
Ferroelectric

Fig: (a) Tetragonal perovskite structure below Tc and the (b) Cubic
structure above Tc

Critical temperature which the spontaneous polarization disappears is

called as Tc: Curie Temperature.
http://www.gitam.edu/eresource/Engg_Phys/semester_2/dielec/B

Piezoelectricity
The word piezo is Greek for push.
What is the definition?
Property of structure to form a polarization, P, under applied
mechanical strain.
Reversible Exhibiting mechanical strain, S, under applied
electric field, E is possible.

Piezoelectricity Effect
Direct piezoelectric effect
the production of an
electric polarization by a
strain
Converse piezoelectric
effect the production of
a stress by an electric field
Fig: (a) Piezoelectric crystal w/o any applied stress or E (b) Direct
piezoelectric effect (c) and (d) Conversed piezoelectricity (The
dashed rectangle is the original sample size in )

Principles of Electronic Materials and Devices, Second Edition, S.O. Kasap ( Mc

Piezoelectricity Effect
Polarization is directly proportional to the stress applied for
direct piezoelectricity,
Eqn 1:

P=d

wherePis polarization,dis piezoelectric coefficient,is

stress.
Strain is proportional to applied E for converse piezoelectricity,
Eqn 2: =dE
whereis strain,dis piezoelectric coefficient,Eis electric
field.
http://www.doitpoms.ac.uk/tlplib/piezoelectrics/polarisati
on.php

Piezoelectricity
Examples

Quartz (SiO2)
Silk
Lead titanate (PbTiO2)*
Barium titanate (BaTiO3)
Lead zirconate (PbZrO3)
Lithium niobate(LiNbO3)

Applications

Transducers such as
ultrasound
Speakers
Microphone
Earphone
Sensors
http://www.doitpoms.ac.uk/tlp
lib/piezoelectrics/applicatio
ns.php

Pyroelectricity
The word pyro is Greek for fire.
What is the definition?
Property of structure to make a spontaneous change in
polarization, due to the thermal effects.

It is a bridge between piezoelectric and ferroelectric.

Fig: Relationship of piezoelectric, pyroelectric and

ferroelectric
http://www.doitpoms.ac.uk/tlplib/piezoelectrics/spontaneou

Pyroelectricity

T increase creates spontaneous polarization.

Examples

Lithium tantalate(LiTaO3)
Polyvnyl fluorides

Applications

Thermal imaging (IR

detection)
Pollutant control

Fig: Pyroelectric crystal with Intrinsic dipole moment and its

reaction to increase in T

http://www.slac.stanford.edu/grp/arb/tn/arbvol5/AAR

Ferroelectricity
The prefix ferro means iron (but not most do not contain
iron).
What is the definition?
Property of structure to have a spontaneous dipole moment
(polarization) which can be reversed by an applied electric
field.
Switchable polarization

Subset of both piezoelectric and pyroelectric materials

Net permanent dipole moment

Hysteresis Loop:

Assume we have fully polarized material.

Aligned dipole moments are affected by reversed E.

Direction of dipole moments changes in time.

Polarization is reversed at the end (until applied E is

removed).

http://www.doitpoms.ac.uk/tlplib/ferroelectrics/switching2.php

Fig: Hysteresis
loop
http://www.ceramicindustry.com/articles/92711-the-world-of-ferroelectric-

Hysteresis Loop:
Temperature dependence
When T increases, hysteresis loop becomes sharper and thinner.

Reasons

Fig: Hysteresis loop for

different T

Disorder which increases with T and decreases net dipole moment

Phase transformations which can create new dipole moments

http://www.doitpoms.ac.uk/tlplib/ferroelectrics/temp_depende

Ferroelectricity
Examples
Barium titanate (BaTiO3) bt.
298-393 K
Rochelle salt bt 255-296 K

Applications

Computer memory
elements
Capacitors

http://www.doitpoms.ac.uk/tlp
lib/ferroelectrics/why.php

Applications and explanation of

ferroelectricity, pyroelectricity
and piezoelectricity

Ferroelectric Materials Applications

Ferroelectric capacitors
o Medical ultrasound machines
o High quality IR cameras
Ferroelectric RAM
Sensors
o Fire sensors
o Vibration sensors
o Sonar Sensors

J.F. Scott (2000). Ferroelectric Memories. Springer. ISBN 3-540-66387-8.

Ferroelectricity: zoomed in a little bit!

https://www.youtube.com/watch?v=-aFm8_nE6bM&list=PLC3582BD2E81221C9

Pyroelectric materials applications

Pyroelectricity can be visualized as one side of a triangle, where each corner represents
energy states in the crystal:
kinetic, electrical and thermal energy.
The side between electrical and thermal corners represents the pyroelectric effect and
produces no kinetic energy.
The side between kinetic and electrical corners represents the piezoelectric effect and
produces no thermal energy.

Buchanan, Relva C. (2004). Ceramic Materials for Electronics: Third Edition, Revised and Expanded (Third ed.). Cincinnati, Ohio: Marcel Dekker, Inc. p. 217. ISBN 0-8247-4028-9.

Pyroelectric materials applications

Applications:
o IR sensors (heat sensors)
o Heat engines (e. g. lowering the operating temperatures, using less bulky equipment, and having
fewer moving parts) can be used in an Ericsson cycle to reach higher levels of Carnot efficiency
Advantages
o Wide thermal and electromagnetic sensitivity
o Fast response (0 to 10 Hz)
o Low-cost
o Work at ambient temperature
Kouchachvili, L; Ikura, M (2007). "Pyroelectric conversionEffects of P(VDFTrFE) preconditioning on power conversion". Journal of Electrostatics 65: 182. doi:10.1016/j.elstat.2006.07.014.

Piezoelectric materials applications

In piezoelectric materials, electrical energy is converted into mechanical energy and/or vice
versa. So, piezoelectricity is used in:
o Speakers
o Microphones
o Solar devices
o Actuators
o High precision positioning with electrical polarization
o Igniters

MAT 408 lecture notes, Prof. Dr. Mehmet Ali Gulgun, Faculty of Engineering and Natural Sciences, Sabanci University, Fall 2015.

Piezoelectric materials applications:

grand mothers part

Perovskite Structure: ABO3

Perovskite structure has a general formula of ABO3
Perovskite is one of the widely found structures in the materials (mostly ceramics) exhibiting
ferroelectricity, pyroelectricity and piezoelectricity or a combination of them.
Perovskites are composed of two different cations and an anion, for which the sizes of cations
differ considerably, like in CaTiO3 (perovskite) perovskite is also the name of CaTiO3 mineral
Where Ca+2 and O-2 form a closed-packed cubic structure, with the smaller cation (Ti+4) in the
octahedral interstitial site at the center of the cube.

MAT 408 lecture notes, Prof. Dr. Mehmet Ali Gulgun, Faculty of Engineering and Natural Sciences, Sabanci University, Fall 2015.

Perovskite Structure: ABO3

Fig. 1. Perovskite
Structure.
MAT 408 lecture notes, Prof. Dr. Mehmet Ali Gulgun, Faculty of Engineering and Natural Sciences, Sabanci University, Fall 2015.

Goldschmidt tolerance factor

o Goldschmidt's tolerance factor indicates the relation of the chemical composition of a perovskite to its stability
o the tolerance factor can be used to calculate the compatibility of an ion with a crystal structure
o The first description of the tolerance factor for perovskite was made by Victor Moritz Goldschmidt in 1926

r is the radius of the A-cation.

A

r is the radius of the B-cation.

B

r is the radius of the anion.

O

Goldschmidt tolerance factor

A practical example of using piezoelectric

materials in new technologies

References
http://www.doitpoms.ac.uk/tlplib/crystallography3/intro.php
http://www.doitpoms.ac.uk/tlplib/crystallography3/lattice.php
http://www.doitpoms.ac.uk/tlplib/crystallography3/unit_cell.php
http://www.aps.anl.gov/Xray_Science_Division/Powder_Diffraction_Crystallography/Introduction_to_Crystallography/#0
3
http://www.doitpoms.ac.uk/tlplib/crystallography3/parameters.php
http://www.doitpoms.ac.uk/tlplib/crystallography3/parameters.php
http://www.doitpoms.ac.uk/tlplib/crystallography3/unit_cell.php
http://www.doitpoms.ac.uk/tlplib/crystallography3/parameters.php
http://chemistrytextbookcrawl.blogspot.com.tr/2012/08/chapter-3.html
http://202.141.40.218/wiki/images/JK-table1.png
http://learn.crystallography.org.uk/learn-crystallography/what-is-a-crystal/
Hummel, R. E. (2011). Electronic Porperties of Materials. New York: Springer.
Moulson, A. J., & Herbert, J. M. (1990). Electroceramics. Cambridge: Chapman&Hall.
Glgn, M.A..(2014). An Introductory Course to Ceramics.
https://www.ucl.ac.uk/qsd/people/teaching/EOPM-Part3.pdf

References
http://www.doitpoms.ac.uk/tlplib/ferroelectrics/phase_changes.php
http://www.doitpoms.ac.uk/tlplib/ferroelectrics/why.php
http://www.gitam.edu/eresource/Engg_Phys/semester_2/dielec/BaTiO3.htm
http://www.nanomotion.com/piezo-ceramic-motor-technology/piezoelectric-effect/
http://www.doitpoms.ac.uk/tlplib/piezoelectrics/polarisation.php
http://www.slac.stanford.edu/grp/arb/tn/arbvol5/AARD459.pdf
http://www.ceramicindustry.com/articles/92711-the-world-of-ferroelectric-ceramics
http://www.doitpoms.ac.uk/tlplib/ferroelectrics/switching2.php
http://academic.uprm.edu/pcaceres/Courses/Smart/SMD-5A.pdf
J. F. Scott (2000). Ferroelectric Memories. Springer. ISBN 3-540-66387-8
https://www.youtube.com/watch?v=-aFm8_nE6bM&list=PLC3582BD2E81221C9
Buchanan, Relva C. (2004). Ceramic Materials for Electronics: Third Edition, Revised and Expanded (Third ed.).
Cincinnati, Ohio: Marcel Dekker, Inc. p. 217. ISBN 0-8247-4028-9
Kouchachvili, L; Ikura, M (2007). "Pyroelectric conversionEffects of P(VDFTrFE) preconditioning on power
conversion". Journal of Electrostatics 65: 182. doi:10.1016/j.elstat.2006.07.014
MAT 408 lecture notes, Prof. Dr. Mehmet Ali Gulgun, Faculty of Engineering and Natural Sciences, Sabanci University,
Fall 2015