GEOMETRY OF CRYSTALS

MATERIALS SCIENCE
 Space Lattices Part of & AALearner’s Guide
Learner’s Guide
ENGINEERING
 Motifs
AN INTRODUCTORY E-BOOK

 Crystal Systems Anandh Subramaniam & Kantesh Balani

Materials Science and Engineering (MSE)
Indian Institute of Technology, Kanpur- 208016
Email: [email protected], URL: home.iitk.ac.in/~anandh
http://home.iitk.ac.in/~anandh/E-book.htm
Advanced Reading
Elementary Crystallography
M.J. Buerger
John Wiley & Sons Inc., New York (1956)
The Structure of Materials
Samuel M. Allen, Edwin L. Thomas
John Wiley & Sons Inc., New York (1999)
Crystallography (2nd Edition)
Walter Borchardt-Ott
Springer, Berlin (1995)
Caution Note: In any chapter, amongst the first few pages (say 5 pages) there will be some ‘big picture’
overview information. This may lead to ‘overloading’ and readers who find this ‘uncomfortable’ may skip
particular slides in the first reading and come back to them later.
What will you learn in this chapter? This chapter is divided into three ‘sub-chapters’ (file structure)*

 In this chapter we shall try to understand a CRYSTAL

 We shall consider some ideal mathematical descriptions before taking up
examples of real crystals (as we shall see these crystals contain atoms, ions or
molecules)
 The use of Miller indices for directions and planes in lattices and crystals
 How to use X-Ray Diffraction for determination of crystal geometry.

* 3.1 Overview, Geometry of Crystals

3.2 Miller Indices
3.3 X-ray Diffraction

Caution Note: In any chapter, amongst the first few pages (say 5 pages) there will be some ‘big picture’
overview information. This may lead to ‘overloading’ and readers who find this ‘uncomfortable’ may skip
particular slides in the first reading and come back to them later.
 What will you learn in this ‘sub-chapter’?
 In this sub-chapter we shall try to understand a CRYSTAL.
 We shall consider some ideal mathematical descriptions before taking up
examples of real crystals (as we shall see these crystals contain atoms, ions or
molecules).
 We will see that the language of crystallography is applicable to all kinds of
crystals (those containing atomic entities, ‘physical properties’ or mathematical ones).
 The real crystals we consider in this chapter are also ‘idealizations’ (i.e. The
crystals found in practice have various kinds of defects in them and we shall
take up topics related to defects in crystals in the chapter on crystal
imperfections (Chapter-5)).
Note the facets

To see other kinds of crystals click here Slide 4 (few slides)

Let us start by looking at crystallization from a melt

(of stearic acid)

Video:
Video:Dendritic
Dendritic
growth
growth ofcrystal
of crystal
from KDP crystals grown from solution
frommelt
melt
 Why study crystal structures?
 When we look around much of what we see is non-crystalline (organic things like
wood, paper, sand; concrete walls, etc.  some of the things may have some crystalline parts!).
 But, many of the common ‘inorganic’ materials are ‘usually*’ crystalline:
◘ Metals: Cu, Zn, Fe, Cu-Zn alloys
◘ Semiconductors: Si, Ge, GaAs
◘ Ceramics: Alumina (Al2O3), Zirconia (Zr2O3), SiC, SrTiO3.
 Also, the usual form of crystalline materials (say a Cu wire or a piece of
alumina) is polycrystalline and special care has to be taken to produce single
crystals.
 Polymeric materials are usually not ‘fully’ crystalline.
 The crystal structure directly influences the properties of the material
(as we have seen in the Introduction chapter many additional factors come in).

Why study crystallography?

 Gives a terse (concise) representation of a large assemblage of species

 Gives the ‘first view’ towards understanding of the properties of the crystal

Click here to see how symmetry helps reduce the information content Slide 6 Also see Slide 9

* Many of the materials which are usually crystalline can also be obtained in an amorphous form
  We shall consider two definitions of a crystal:
1) Crystal = Lattice + Motif [Lattice decorated with a motif]
2) Crystal = Space Group + Asymmetric unit (+Wyckoff positions)*.
 The second definition is the more advanced one (the language of
crystallographers) and we shall only briefly consider it in this
introductory text.
 The second definition becomes important as the classification of crystals
(7 crystal systems) is made based on symmetry and the first definition
does not bring out this aspect.
 Note: Since we have this precise definition of a crystal, loose definitions
should be avoided (Though often we may live with definitions like: a 3D translationally
periodic arrangement of atoms in space is called a crystal).
 Initially we shall start with ideal mathematical crystals and then slowly
we shall relax various conditions to get into practical crystals.
Note: ‘+’ above does not imply simple addition! It implies a lattice decorated with a motif.
More technically it can be thought of as a convolution operation.

*Actually, the space group in combination with the Wyckoff positions will do the job (give us the whole crystal).

The language of crystallography is one succinctness

 Ideal Crystals → Real Crystals → Microstructures → Material → Component
Ideal Crystal
Ideal Mathematical Crystal Some of these
aspects will be
Consider only the Geometrical Entity considered in
or detail later
only the Physical Property
Crystal* Consider only the Orientational
or
Positional Order
Crystal**
Put in Crystalline defects
& Free Surface
& Thermal Vibration
‘Real Crystal’
Put in Multiple Crystals (Phases)
giving rise to interfacial defects
~Microconstituents
Put multiple ~microconstituents
Add additional residual stress
Real materials are
Microstructure usually complex and we
start with ideal
descriptions
MaterialMaterial or Hybrid

*, ** Reduced definition of crystals

Component
 That which is NOT associated with defects (crystalline or interfacial) → e.g. thermal residual stresses
 Ideal Crystals → Real Crystals → Microstructures → Material → Component
ometrical entity

ysical Property
Ideal Crystal
Ideal Mathematical Crystal

Consider only the Geometrical Entity Part of the infinite crystal

or
only the Physical Property

Crystal*
Part of the infinite crystal
Consider only the Orientational
or
Positional Order

a iled Crystal**
et
Ad k
loo Part of the infinite crystal

Put in Crystalline defects

& Free Surface
& Thermal Vibration

Vacancy shown as an example of a defect

‘Real Crystal’
*, ** Reduced definition of crystals
Ideal Crystals → Real Crystals → Microstructures → Material → Component
Ideal Mathematical Crystal
Ideal Crystal
Some of these
(Considers both Geometrical Entity AND Physical Property/) aspects will be
considered in
Crystal* detail later

(Here we consider either geometrical entity OR physical property)

Crystal**
(Consider either the Orientational OR the Positional Order)

‘Real Crystal’
(Presence of Crystalline defects & Free Surface & Thermal Vibration)

~Microconstituents
(Put in Multiple Crystals (Phases) giving rise to interfacial defects)

Microstructure
(Put in multiple ~microconstituents and add additional residual stress )

Material
(Put in many microstructures)

Component
(Put in material/s and/or material treatment i.e. temperature/pressure)
*, ** Reduced definition of crystals
 That which is NOT associated with defects (crystalline or interfacial)
Definition 1

Crystal = Lattice + Motif

Motif or Basis:
an entity (typically an atom or a group of atoms) associated with each lattice point

Lattice  the underlying periodicity of the crystal

Motif  Entity associated with each lattice point

Lattice  how to repeat

Motif  what to repeat

Lattice Crystal
Translationally periodic Translationally periodic
arrangement of points arrangement of motifs
 Definition 1
Crystal =
Lattice (Where to repeat)
+
Motif (What to repeat)
Crystal



a
=
Lattice


a
+
Motif Note: all parts of the motif do not sit on the lattice point
a
2 e.g.

Slide 12
Motifs are associated with lattice points
 they need NOT sit physically at the lattice point

Note: Later on we will also consider cases wherein these arrow marks are replaced with atomic entities
 Let us construct the crystal considered before starting with an infinite array of
Funda Check points spaced a/2 apart

This array of points also forms a lattice.

Fig.1 Lattice parameter for this lattice is a/2.

Put arrow marks pointing up and down alternately on the points:

Fig.2

 as this lattice parameter is a

What we get is a crystal of lattice parameter ‘a’ and not ‘a/2’! measure of the repeat distance!

And the
motif is:
+
Fig.3

Note: the lattice in Fig.1 is not the

lattice for the crystal in Fig.3
Note that only these alternate points
have identical surroundings

Note: we could have alternately chosen the centres of bottom arrows as lattice points!
Space LatticeA lattice is also called a Space Lattice (or even Bravais Lattice in some contexts)

An array of points in space such that every point has identical

surroundings Note: this is the proper definition of a lattice

 This automatically implies two properties of lattices

 In Euclidean space lattices are infinite (infinite array)
 Lattices ‘have translational periodicity’
or
Translationally periodic arrangement of points in space is called a lattice*

 We can have 1D, 2D or 3D arrays (lattices)

The motif associated with these lattices can themselves be 1D, 2D or 3D ‘entities’.

* this definition arises naturally from the first definition.

Note: points are drawn with finite size for clarity  in reality they are 0D (zero dimensional)
Definition 2
Crystal =

This is a advanced
Space group (how to repeat)
definition
‘Just for
information’
+
Readers can skim through this slide
Asymmetric unit (Motif’: what to repeat)
+Wyckoff positions

a
=
Glide reflection
a operator
Symbol g may also be used

+ Positions entities
with respect to
symmetry operators

+Wyckoff label ‘a’

Usually asymmetric units are regions of space- which contain the entities (e.g. atoms)
 Q&A What properties/characteristics of the crystal arise from the definitions (considered earlier)?

 Crystals are endowed with the following characteristics.

 Crystals are periodic.
 Crystals are infinite (in Euclidian space). (Practical crystals are finite!).
 Crystals have orientational and positional order.
 Many/most crystals have additional symmetries associated with them (we will see this
soon).

 Additionally:
 Crystals may be anisotropic with respect to many of the properties.
 Have well defined equilibrium shapes (at low temperatures), which reflect the internal
symmetry present at the atomic level.
As mentioned before crystals are understood based on the language of symmetry

 Symmetry is perhaps the most important principle of nature:

 though often you will have to dig deeper to find this statement
 The analogous terms to symmetry are:
Symmetry  Conservation  Invariance
 The kind of symmetry of relevance to crystallography is geometrical
symmetry

 The kind of symmetry we encountered in the definition of a lattice is

TRANSLATIONAL SYMMETRY (t)
To know more about symmetry and its role in the definition of crystal
structures click here (Very Important!!)
 Now let us make some crystals
(to see more examples click here)
Making a 1D Crystal
 Some of the concepts are best illustrated in lower dimensions  hence we shall
construct some 1D and 2D crystals before jumping into 3D
 A strict 1D crystal = 1D lattice + 1D motif
 The only kind of 1D motif is a line segment

 An unit cell is a representative unit of the structure (finite part of an infinite

structure)
 which when translationally repeated gives the whole structure.

Lattice

+
Motif
=

Crystal
Other ways of making the same crystal
 We had mentioned before that motifs need not ‘sit’ on the lattice point- they are
merely associated with a lattice point
 Here is an example:

Note:
For illustration purposes we will often relax this strict requirement of a 1D motif
 We will put 2D motifs on 1D lattice to get many of the useful concepts across
(Actually we have already done this in the example considered before  with
an up arrow () and a down arrow ())

1D lattice +
2D Motif*

*looks like 3D due to the shading! It has been shown in literature that 1D crystals cannot be stable!!
Making a 2D Crystal
 Some aspects we have already seen in 1D  but 2D many more concepts can be
clarified in 2D
 2D crystal = 2D lattice + 2D motif
 As before we can relax this requirement and put 1D or 3D motifs!
(to know more about motifs click here)

Continued
 Lattice


Motif

 + 


b



a
Continued
 Crystal r The 2D crystal (& lattice) is
| b |= b


specified using 3 lattice
       | ar |= a parameters: ‘a’, ‘b’ and α.
a
      
As before there are many
=        ways of associating the
motif with a lattice point
        (one of these is shown)


      
      
In many places the ‘infinity’ will be left out
(it is implied)
      
       For objects with circular symmetry in 2D and


spherical symmetry in 3D there is no need to

‘worry about’ orientational order!

Note:
Each motif is identically oriented (orientationally ordered)
and
is associated exactly at the same position with each lattice point (positionally ordered)
We will have more to say on this in Chapter 4
Funda Check What is meant by the statement that motif is ‘associated’ with the lattice point?

 Motif is associated with the lattice point and need not ‘sit’ on the lattice point. In any case
the full motif cannot ‘sit’ on the lattice point (just one point, maybe the centroid of an
object, can ‘sit’ on the lattice point).
 Motif can be associated with a lattice point in many ways, as in the examples below*.
 In some cases the motif may consist of many atoms, but in the natural choice of association
with a lattice point, none of the atoms ‘sit’ at the lattice point: (i) in the Fullerene crystal
with 60 carbon atoms per molecule (the motif) none of the carbon atoms are at the lattice
point; (ii) in -brass there are 26 atoms in the motif (Cu10Zn16) (and 52 in the UC), but none
of them are at the lattice point.

In all the cases the

conventional unit cell
is marked in orange

* As obvious, there are infinite number of ways of making this crystal!

Now let us make some more 2-D crystals
Click
here
Making a 3D Crystal
 3D crystal = 3D lattice + 3D motif.
 There are 14 distinct lattices possible in 3D called the Bravais lattices.
Crystal system
 Lattices can be constructed using translation alone.
 The definition (& classification) of Crystals is based on symmetry and NOT on
the geometry of the unit cell (as often one might feel after reading some books!).
 Crystals based on a particular lattice can have symmetry:
 equal to that of the lattice or
 lower than that of the lattice.
 Based on symmetry crystals are classified into seven types/categories/systems
known as the SEVEN CRYSTAL SYSTEMS.
 We can put all possible crystals into 7 boxes based on symmetry.

Alternate view Advanced concept: readers can return to this point later!

 Symmetry operators acting at a point can combine in 32 distinct ways to give the
32 point groups.
 Lattices have 7 distinct point group symmetries which correspond to the SEVEN
CRYSTAL SYSTEMS.
 If the definition/classification of Crystals (e.g. cubic crystal) is based on
Funda Check
symmetry and the existence of 7 crystal systems is also based on symmetry; then
how come we have statements like: a = b = c, a =  =  = 90 is a cubic crystal?

 This is an important point and requires some clarification.

 Though the definition of crystals (e.g. cubic crystals) are based on symmetry and
NOT on the geometry of the unit cell; it is true that if we already have cubic
crystal it is most preferred/logical to use parameters like
a = b = c, a =  =  = 90.
 The next slide explains as to why a set of coordinate axis is more preferred for certain
geometrical entities using the example of a circle.
 Also see hyperlink below.

Relation between geometry and symmetry in atomic crystals

 Concept of symmetry and choice of axes

( x  a ) 2  ( y  b) 2 = r 2
(a,b)
The centre of symmetry
of the object does not
coincide with the origin Polar coordinates (, )

 =r
( x)  ( y ) = r
2 2 2

The circle is described equally well by the three

The type of coordinate equations; but, in the polar coordinate system
(with centre of the circle coinciding with the
system chosen is not origin), the equation takes the most elegant
according to the symmetry (simple) form
of the object

Our choice of coordinate axis does not alter the symmetry of the object (or the lattice)!
 What are the symmetries of the 7 crystal systems?
 Minimum symmetry of the 7 crystals systems are listed in the table below.
 As an example: cubic crystals have four 3-fold axes (at least), while a trigonal crystal has
only one 3-fold axis (but can have other symmetries). Tetragonal crystals have one 4-fold
axis at least (but cannot have three 4-fold axes).
The characteristic symmetry refers to the minimum
symmetry that needs to be present.

We have stated that basis of definition of

crystals is ‘symmetry’ and hence the
classification of crystals is also based on
symmetry.
The essence of the required symmetry is
listed in the table
 more symmetries may be part of the
point group in an actual crystal.

Note that the symmetry being considered is the

point group symmetry. The translational
components are ‘dropped’ while noting the
symmetry. E.g. 63 screw axis is written as a ‘6’.
(only translational symmetry)

Note: translational symmetry is always present in crystals (i.e. even in triclinic crystal)
14 Bravais Lattices divided into 7 Crystal Systems Refer to slides on Lattice for more on these

A Symmetry based concept ‘Translation’ based concept

Crystal System Shape of UC Bravais Lattices

P I F C
1 Cubic Cube   
2 Tetragonal Square Prism (general height)  
3 Orthorhombic Rectangular Prism (general height)    
4 Hexagonal 120 Rhombic Prism 
5 Trigonal Parallelepiped (Equilateral, Equiangular) 
6 Monoclinic Parallogramic Prism  
7 Triclinic Parallelepiped (general) 

P Primitive
Why are some of the entries missing? I Body Centred
 Why is there no C-centred cubic lattice?
 Why is the F-centred tetragonal lattice missing? F Face Centred
 ….? C A/B/C- Centred
 THE 7 CRYSTAL SYSTEMS
Some general notes on the frequency of occurrence of various crystal systems
 In metals the high symmetry cubic & hexagonal systems are more common, while in organic
systems the low symmetry ones are more common (as expected it is difficult to pack the
complicated organic molecules into a high symmetry configuration).
 1. Name of crystal system
Orientation of
lattice parameters and Diagram of property axes w.r.t
relationship amongst preferred UC to UC*
them
(preferred Unit Cell)

• Possible Bravais lattices

Point groups belonging to the crystal system

* When various properties are measured these are the axes along which the values are tabulated
Note on understanding point groups Click here to know more about symmetry and point groups

 Typically the topic of point groups is advanced for a elementary course. However, if
interested one can refer to the chapter on symmetry first.
 In the symbol for the point group there is a maximum of 3 positions as in the example
below.
4 2 Symmetry directions in the seven
Cubic pointgroup � 3 crystal systems
m m
<a> <111> <110>

 These correspond to well defined crystallographic

directions as in the table. As usual these brackets
< > refer to the family of directions.

* Few trigonal space groups have <210> as the 3rdrd

symmetry direction (similar to hexagonal system).
E.g. P312.
1. Cubic Crystals
a = b= c
a =  =  = 90º

Orientation of property axes

orthogonal set (Z1, Z2, Z3)

• Simple Cubic (P) - SC

SC, BCC, FCC are lattices
• Body Centred Cubic (I) – BCC
while HCP & DC are crystals!
• Face Centred Cubic (F) - FCC

2 4 2
Point groups � 23, 43m, 3, 432, 3
m m m Note the 3s are in the second position

 Elements with Cubic structure → SC: F, O, Po Note: Ge has two atoms per lattice
point (has DC crystal structure
BCC: Cr, Fe, Nb, K, W, V
Note: here SC, BCC & FCC are lattices
FCC: Al, Ar, Pb, Ni, Pd, Pt, Ge
Examples of elements with Cubic Crystal Structure
 Depending on the type of lattice and the motif the number of atoms per unit cell can vary.

Fe Cu
Po

n=1 SC n=2 BCC n = 4 FCC/CCP n=8 DC

C (diamond)
 Examples of few crystal shapes (cubic crystal system)
Crystal Shape

 In well grown (eumorphic) and ‘equilibrated’ crystals the inherent point group symmetry
(not that translations involved in space group symmetry are not relevant at this length scale)
is expressed in the external shape (form) of the crystals.
 Hence, cubic crystals can have equilibrium shapes which include: cube, octahedron,
truncated octahedron, tetrahedron (for 23 point group crystals), etc.

The shape of the crystal (Eumorphic- well formed) will

‘reflect’ the point group symmetry of the crystal

Tetrakaidecahedron
Cube Octahedron Tetrahedron (Truncated Octahedron)
 Note that cubic crystals can have the shape of a cube, an octahedron, a truncated octahedron
etc.
(some of these polyhedra have the same rotational symmetry axes; noting that cube and
octahedron are regular solids (Platonic) while truncated octahedron with two kinds of faces
is not a regular solid)
 The external shape is a manifestation (‘reflection’) of the symmetry at the atomic level.
 Point groups have been included for completeness and can be ignored by beginners.
 Cubic crystals can be based on Simple Cubic (SC), Body Centred Cubic (BCC) and Face
Centred Cubic Lattices (FCC)
 by putting motifs on these lattices.
 After the crystal is constructed based on the SC, BCC or FCC lattice, it should have four 3-
fold symmetry axes (along the body diagonals)
 which crystals built out of atomic entities will usually have
 if the crystal does not have this feature it will not be a cubic crystal (even though it is
based on a cubic lattice).
2. Tetragonal Crystals
a=bc
a =  =  = 90º

• Simple Tetragonal
• Body Centred Tetragonal -BCT
Orientation of property axes
orthogonal set (Z1, Z2, Z3)

4 4 2 2
Point groups  4, 4, , 422, 4mm, 4 2m,
m mmm

 Elements with Tetragonal structure → In, Sn Note the 4 in the first place
In Example of an element with Body Centred Tetragonal Crystal Structure

[100] views

BCT

All atoms are In → coloured

for better visibility

In [001] view
Lattice parameter(s) a = 3.25 Å, c = 4.95 Å
Space Group I4/mmm (139)
Strukturbericht notation A6 Wyckoff Site
x y z Occupancy
position Symmetry
Pearson symbol tI2
In 2a 4/mmm 0 0 0 1
Other examples with this structure Pa
Note: All atoms are identical (coloured differently for easy visualization)
 3. Orthorhombic Crystals
abc
a =  =  = 90º
• Simple Orthorhombic
• Body Centred Orthorhombic
• Face Centred Orthorhombic
• End Centred Orthorhombic Orientation of property axes
(note: the only lattice with all possibilities present) orthogonal set (Z1, Z2, Z3)

Usual convention
cab
2 2 2
Point groups  222, 2mm,
mmm

 Elements with Orthorhombic structure → Br, Cl, Ga, I, S, U

Ga Example of an element with Orthorhombic Crystal Structure

[010] view

[001] view

Ga
Lattice parameter(s) a = 2.9 Å, b = 8.13, c = 3.17 Å
Wyckoff Site
Space Group Cmcm (63) x y z Occupancy
position Symmetry
Strukturbericht notation
Ga 4c m2m 0 0.133 0.25 1
Pearson symbol oC4
Note: All atoms are identical (coloured differently for easy visualization)
4. Hexagonal Crystals
a=bc
a =  = 90º  = 120º

• Simple Hexagonal
(note: there is only one type of
hexagonal lattice)

Orientation of property axes

orthogonal set (Z1, Z2, Z3)

 Note that the unit cell is not the hexagonal prism, but the blue shaded rhombic prism. This
unit cell does not have the hexagonal symmetry and hence we often show a compound of 3
unit cells (as above), which has 6-fold symmetry.

6 6 2 2
Point groups  6, 6 , , 622, 6mm, 6 m2,
m mmm

Click here to know more about

 Elements with Hexagonal structure → Be, Cd, Co, Ti, Zn HCP crystals

* Note: note HCP is one type of a crystal having a hexagonal lattice (with two identical atom motif). We will discuss this soon.
 Mg Example of an element with Hexagonal Crystal Structure

This is a HCP structure

(it has only a 3-fold pure rotation
axis along z-direction, along ‘z’ it
has a 63 screw axis)

More about this in the chapter on

Structure_of_Solids_Metallic
Note: All atoms are identical (coloured differently for easy visualization)
 Some times an alternate hexagonal cell
. Trigonal/Rhombohedral Crystals is used instead of the Trigonal Cell
a=b=c
a =  =   90º

Rhombohedral (simple)

2
Point groups  3, 3 , 32, 3m, 3
m
Note the 3s are in the first position

 Elements with Trigonal structure → As, B, Bi, Hg, Sb, Sm

Video:
Video:Cubic
CubictotoTrigonal
Trigonalunit
unitcell
cell
 Example of an element with Simple Trigonal Crystal Structure
a-Hg

[111] view

a-Hg
Lattice parameter(s) a = 3.005 Å
Space Group R-3m (166)
Strukturbericht notation A10
Wyckoff Site
x y z Occupancy
Pearson symbol hR1 position Symmetry
Other examples with this structure -Po Hg 1a -3m 0 0 0 1
6. Monoclinic Crystals
abc
a =  = 90º  

• Simple Monoclinic
• End Centred (base centered)

Monoclinic (A/C)

2
Point groups  2, 2 ,
m
The ‘b’ axis is along the 2 or 2bar or 
m
Orientation of property axes
 Elements with Monoclinic structure → P, Pu orthogonal set (Z1, Z2, Z3)
7. Triclinic Crystals
abc
a  

• Simple Triclinic

Point groups  1, 1

Orientation of property axes

orthogonal set (Z1, Z2, Z3)
 Note that cubic crystals can have the shape of a cube, an octahedron, a truncated octahedron
etc. (all these polyhedra have the same symmetry; noting that cube and octahedron are
regular solids (Platonic) while truncated octahedron with two kinds of faces is not a regular
solid).
 The external shape is a ‘reflection’ of the symmetry at the atomic level.
 Point groups have been included for completeness and can be ignored by beginners.
 Cubic crystals can be based on Simple Cubic (SC), Body Centred Cubic (BCC) and Face
Centred Cubic Lattices (FCC)
 by putting motifs on these lattices.
 After the crystal is constructed based on the SC, BCC or FCC lattice, it should have four 3-
fold symmetry axes (along the body diagonals)
 which crystals built out of atomic entities will usually have
 if the crystal does not have this feature it will not be a cubic crystal (even though it is
based on a cubic lattice)  more on this here.
Now let us consider some simple crystals
Simple Cubic (SC) Lattice + Sphere Motif
Graded Shading to give 3D effect

Unit cell of the SC lattice Simple Cubic Crystal

 If these spheres were ‘spherical atoms’ then the atoms would be touching each other
 The kind of model shown is known as the ‘Ball and Stick Model’
Click here to know more about the kind of models used to represent crystal structures
A note on kind of models used for representation of Crystal Structures

Wire Frame model Ball & Stick Model

Atoms are reduced to points and the Both atoms & cell edges are in view
focus is on the cell edges (but atoms do not touch each other)

Cubic void
Void Models

Space Filling Model

Where the void (actually the polyhedron

Atoms touch each other. formed by the vertices of the void) is in full
Unit cell edges may not be visible view and everything else is hidden away
Note: though these are called space filling models in reality they do not fill space
[as obvious from the space between the atoms (-the voids)]
 Body Centred Cubic (BCC) Lattice + Sphere Motif

Atom at (½, ½, ½)

Body Centred Cubic Crystal

Atom at (0, 0, 0)
=
Unit cell of the BCC lattice

Space filling model

So when one usually talks about a BCC crystal what is meant is a BCC
Central atom is coloured differently for better visibility lattice decorated with a mono-atomic motif

Note: BCC is a lattice and not a crystal Video:

Video:BCC
BCCcrystal
crystal
 All atoms are identical- coloured differently for better visibility

Face Centred Cubic (FCC) Lattice + Sphere Motif

Cubic Close Packed Crystal

Atom at (½, ½, 0) (Sometimes casually called the FCC crystal)
Atom at (0, 0, 0)

=
Unit cell of the FCC lattice

Space filling model

So when one talks about a FCC crystal what is meant is a FCC lattice
decorated with a mono-atomic motif

Note: FCC is a lattice and not a crystal Video:

Video:FCC
FCCcrystal
crystal
 Face Centred Cubic (FCC) Lattice + Two Ion Motif

NaCl Crystal

Cl Ion at (0, 0, 0) Na+ Ion at (½, 0, 0)

Note: This is not a close packed crystal Has a packing fraction of ~0.67 (using rigid sphere model)
Solved example: packing fraction of NaCl

Note that the two ion motif leads to crystal which is not close packed unlike the mono-
Video:
atomic (sphere) packing case Video:NaCl
NaClcrystal
crystal
 Face Centred Cubic (FCC) Lattice + Two Carbon atom Motif
(0,0,0) & (¼, ¼, ¼)

Diamond Cubic Crystal

=

Tetrahedral bonding of C
(sp3 hybridized)

It requires a little thinking to convince yourself that

the two atom motif actually sits at all lattice points!

Note: This is not a close packed crystal Video:

Video:Diamond
Diamondcrystal
crystal
There are no close packed directions in this crystal either!
Emphasis
 For a well grown crystal (eumorphic crystal) the external shape ‘reflects’ the
point group symmetry of the crystal
 the confluence of the mathematical concept of point groups and practical
crystals occurs here!
 The unit cell shapes indicated are the conventional/preferred ones and alternate
unit cells may be chosen based on need
 It is to be noted that some crystals can be based on all possible lattices
(Orthorhombic crystals can be based on P, I, F, C lattices); while others have a
limited set (only P triclinic lattice)  more about this is considered in here
 Next (two slides) we shall try to order the 7 crystal systems based on:
 Symmetry and
 the expenditure in terms of lattice parameters (terseness)
 Then we shall put the 32 point groups into the 7 boxes (7 crystal systems)
Though this task is a little advanced for this elementary treatment
- it brings out the concept that a given crystal type like cubic crystal does not
involve just one symmetry (point group)
- cubic crystals can have lower symmetry than the lattices they are built on
(cubic lattices4have
3
2
symmetry
m m
- we can have cubic crystals without a (pure) 4-fold axis! (e.g. Diamond Cubic
crystal does not have a 4-fold it has a 4 axis)
 The concept of terseness is explained in a subsequent slide
Ordering the 7 Crystal Systems: Based on Symmetry (the order of the point group)
Progressive lowering of symmetry amongst the 7 crystal systems
Order of the point group
of the lattice
Order
Cubic48 Cubic

Hexagonal24 Hexagonal
Increasing symmetry

Tetragonal16
Tetragonal
Trigonal 12

Trigonal
Orthorhombic8
Orthorhombic
Monoclinic4
Monoclinic

Triclinic2 Triclinic

Arrow marks lead from supergroups to subgroups

Superscript to the crystal system is the order of the point group of the lattice
(as crystals based on the lattice can have a lower symmetry)
Ordering the 7 Crystal Systems: terseness

 As we have noted before, when it comes to crystals symmetry is of paramount importance

 However, we have also seen that a given crystal is ‘best’ described by a certain choice of
axes (lattice parameters)
 The next slides describes how the lattice parameters can be used to order the seven crystal
systems
 To do this a parameter called terseness (t) is defined as:
t = (p’  c)
Where, p’ = (p  e)
e → number of ‘=’ amongst the lattice parameters (e.g. in cubic crystals: a = b = c; a =  =   e = 4)
c → number of constraints (numerical) on lattice parameters (e.g. in cubic crystals a, ,  = 90  c = 1)
 Terseness (t) is a measure of ‘how much do we spend’ on lattice parameters!
 The more we spend (larger ‘t’ number) → the lower down it is in the order
The less we spend (small ‘t’ number) → the ‘terser’ we are → higher up in the list

E.g. for Hexagonal: there are 6 parameters (p) and 2 “=“ amongst them (e)
 p’ = (p  e) = (6  2) = 4
c the number of numerical constraints on values is 2 ( a,  = 90;  = 120)
t = (p’  c) = (4  2) = 2
Calculations

t = p  (e + c)
p p’
Crystal System e c (e + c) or
(in 3D) =pe
t = p’  c
Cubic 6 4 2 1 5 1
Tetragonal 6 3 3 1 4 2
Hexagonal 6 2 4 2 4 2
Trigonal 6 4 2 0 4 2
Orthorhombic1 6 2 4 1 3 3
Orthorhombic2 6 2 4 1 3 3
Monoclinic 6 1 5 1 2 4
Triclinic 6 0 6 0 0 6

• (e + c) → is a measure of ‘how much help’ is available via constraints

Progressive relaxation of the constraints on the lattice parameters amongst the 7 crystal systems
E.g. for Cubic: there are 6 parameters (p) and 4 “=“ amongst them (e)
Cubic (p’ = 2, c = 1, t = 1)  p’ = (p  e) = (6  4) = 2
c the number of numerical constraints on values is 1 (= 90)
a=b=c
t = (p’  c) = (2  1) = 1
a =  =  = 90º

Tetragonal (p’ = 3, c = 1 , t = 2) Hexagonal (p’ = 4, c = 2 , t = 2) Trigonal (p’ = 2, c = 0 , t = 2)

a=bc a=bc a=b=c
a =  =  = 90º a =  = 90º,  = 120º a =  =   90º
Increasing number t

Orthorhombic1 (p’ = 4, c = 1 , t = 3) Orthorhombic2 (p’ = 4, c = 1 , t = 3)

abc a=bc
a =  =  = 90º a =  = 90º,   90º

Monoclinic (p’ = 5, c = 1 , t = 4) • p’ = number of independent parameters = p  e

abc (discounting the number of =)
a =  = 90º,   90º • c = number of constraints (positive  “= some number“)
• t = terseness = (p’  c)
(is a measure of the ‘expenditure’ on the parameters
Triclinic (p’ = 6, c = 0 , t = 6)
abc Orthorhombic1 and Orthorhombic2 refer to the two types of cells
a      90º
Click
Click here
here to
to know
know more
more about
about the
the two
two Orthorhombic
Orthorhombic settings
settings
 Minimum symmetry requirement for the 7 crystal systems
This slide is best understood after reading the slides on symmetry
Examples of crystals in the 32 point groups

Minimum
symmetry for
the point
groups
Statistics for the 32
crystallographic point
groups gathered from
more than 280,000
chemical compounds
(by G. Johnson)
Ideal versus Real crystals

 Ideal crystals may have perfect positional and orientational order with respect to
geometrical entities and physical properties.
 In (defining) real crystals some of these strict requirements may be relaxed:
 the order considered may be only with respect to the geometrical entity
 the positional order may be in the average sense
 the orientational order may be in the average sense.
 In addition real crystals:
 are finite
 may contain other defects (Chapter 5).
 Revision of previous slide:

CRYSTALS

Orientational Order Positional Order

Later on we shall discuss that motifs can be:

MOTIFS

Geometrical entities Physical Property

In practice some of the strict conditions imposed might be relaxed and we might
call something a crystal even if :
 Orientational order is missing
 There is only average orientational or positional order
 Only the geometrical entity has been considered in the definition of the crystal
and not the physical property.
 Allotropy, Polymorphism, Isomorphism & Amorphous
 The term “morphous” comes from: Late Latin -morphus –morphous or from Greek –
morphos  which refers to form or shape.
 Allotropy  existence of an element in more than one crystal structure.
 E.g. Fe in CCP (high temperature, ) and BCC (low temperature, a) forms.
 Polymorphism  existence of a crystalline compound in more than one crystal structure.
 E.g. 3C-SiC (cubic) and 2H-SiC (Wurtzite, hexagonal)*.
 Isomorphism  existence of different materials in same crystal structure.
 E.g. Ni and Cu in CCP (FCC).
 Amorphous  having no crystal structure (~glass).
 E.g. Window pane silicate glass.

 Poly-amorphism  existence of a more than one type of amorphous structure.

 E.g. in Y2O3 – Al2O3 amorphous solutions.

* This is according to the Ramsdell Notation.

SUMMARY
 Crystal = Lattice + Motif
 There are 14 Bravais lattices in 3D (which are based on translation)
 Motif is any entity (or entities) which is positioned identically with respect to
every lattice point
 There are 32 different ways in which symmetries (rotation, roto-inversion,
mirror, inversion) can combine at a point called the 32 point groups
 These Bravais lattices have 7 different symmetries which correspond to the 7
crystal systems
 Conventionally, 7 different unit cells are chosen for these 7 crystal systems
 Real crystals are ‘defected’ in many ways so that some of the symmetries present
in an ideal crystal are ‘disturbed’ (either locally or globally).
Funda Check

 The definition of crystals are based on symmetry and not on the geometry of the
unit cell.
 Our choice of unit cell cannot alter the crystal system a crystal belongs to.
 Crystals based on a particular lattice can have symmetry equal to or lower than
that of the lattice.
 When all symmetry (including translation) is lost the construct is called
amorphous.

 Often similar sounding’’ acronyms can be confusing.

 SC, BCC, FCC are lattices.
 DC, HCP are crystals.
 In the space group symbol for crystals with a SC lattice the alphabet ‘P’ is used (e.g.
Pm3m for the B2 structure). (This should not be confused with ‘primitive’. The term
primitive is used in conjunction with an unit cell, while the term simple is used
to designate a type of lattice).
 The alphabet ‘I’ is used for body centred lattices (e.g. Im3m), ‘F’ for face centred
lattices ((e.g. Fm3m) and ‘C’ for end centred lattices (e.g. C2/c).
Funda Check What is a cubic crystal? (or more formally, ‘define a cubic crystal’)

 A cubic crystal is one having at least Four 3-fold axes of rotational symmetry (along the
<111> directions).
 The symmetry along <111> maybe higher: they can be roto-inversion axis: 3 .
 A cubic crystal may or may not have 4-fold axes of symmetry!
 If you have a cubic crystal, then you may (i.e. may not also!) chose axes as (preferred):
a = b = c; a =  =  = 90º (but then you are allowed to make other choices!)
 A cubic crystal should be defined based on symmetry and not the geometry of the unit cell.
 A cubic lattice (SC, BCC, FCC) will have 4 2 point group symmetry (the highest possible
3
symmetry for cubic systems). m m
This is also the symmetry of crystals like Po (based on SC lattice), Cr (based on BCC
lattice, Cu (based on FCC lattice).
2
 Cubic crystals can have lower symmetry as well (e.g. 23, 43m, 3, 432 )
m

 Note that in the point group symbol of cubic crystals the ‘3’ is placed in the second
position.
 An end centred (or C-centred) cubic lattice is not possible, as this will destroy the 3-fold
axes.
 Q&A

 What is a crystal?
 Crystal = Lattice + Motif
 Crystal = Asymmetric Unit + Space Group (+ Wyckoff Positions)
 An array of entities in space, having at least translational symmetry
 What constitutes a motif?
 A geometrical entity or a physical property or a combination of both can serve a motif
 How is the classification of crystals made into the 7 crystal system?
 The classification is purely based on symmetry
 E.g. if a crystal has only one 4-fold axis then it would be classified as a tetragonal crystal
 This classification is not based on geometry of the unit cell (as commonly perceived)
 Ofcourse if one has a cubic crystal, then it will be referred to the cubic axis system
 What are the 14 Bravais lattices?
 There are only 14 different ways in which points can be arranged in 3D space such that each point
has identical surrounding
 What is the relation between the 7 crystal systems and the 14 Bravais lattices?
 Based on symmetry the 14 Bravais lattices can be put into 7 boxes → the 7 crystal systems
 E.g. all lattices with two/four 3-fold axes are put into the box labeled ‘cubic’
 What is the relation between the symmetry of a crystal and the symmetry with respect to its
properties?
 The properties of a crystal can have a symmetry equal to that of the crystal or a symmetry higher
than that of the crystal*
 E.g. cubic crystals (say with 4/m 3 2/m symmetry) have a spherical symmetry w.r.t. to refractive index.

* deriving the actual symmetry is an advanced topic and will not be considered for now
 Solved This example pertains to the decoration of 1-dimensional lattice
Example
1 with a two dimensional object.
An infinite one dimensional array of points are spaced equally with spacing ‘a’

An infinite array of equally spaced points

 
a Shape of the object to be placed at each point: 

 Place an object having the shape of an arrow mark (e.g. ) at each point to create a crystal
of lattice parameter ‘3a’
 Describe this crystal in terms of a Lattice and a Motif
 How is the symmetry altered on the formation of a crystal?
Solution

Method-1

As the shape only has been specified we can use arrow marks of different sizes

3a

Motif: Note: there are an infinite set of possibilities here

Method-2

As the shape only has been specified we can use arrow marks of different colours

3a

Motif: Note: there are an infinite set of possibilities here

Method-3

As the shape only has been specified we can use arrow marks in different orientations

3a

Motif: Note: there are an infinite set of possibilities here

• How is the symmetry altered on the formation of a crystal?

 In the above cases the translational symmetry is lowered from ‘a’ to ‘3a’.
 The array of points have a translational symmetry of ‘a’
→ on formation of the crystal only every third point is a lattice point &
the repeat distance of the crystal is ‘3a’.
 Increase in the length of the translational symmetry vector can be conceived as a reduction in
the symmetry
  Does the array of points at the centres of the Carbon atoms in the graphene sheet as
Solved shown below form a lattice?
Example  Describe the crystal in terms of a lattice and a motif.
2
 What is the unit cell?
Part of the hexagonal array of C atoms which
forms the Graphene structure

The answer is NO!

Not all carbon positions form
a lattice

Crystal = Lattice + Motif

Grey atoms sit on the lattice

positions As atoms A & B do not have
identical surrounding both cannot
Motif = 1 grey + 1 green be lattice points
(in positions as shown)

Primitive unit cell

Funda Check List all the crystal systems, their preferred unit cells, along with the
points groups belonging to these crystal systems
 Q&A What are the various symbols used in
crystallography?
 Typically the symbols used are:
(i) Strukturbericht notation (which is based on listing),
(ii) Pearson symbol,
(iii) Point/space group symbol/number.
Sometimes structure type is also used to designate a crystal.
 Let us take the example of β-Mn below.
Space group
-Mn
Space group number
Lattice parameter(s) a = 6.3145 Å
Space Group P4132 (213) ‘P’ is for primitive
Point Group 432 Drop the translational components to get point group
A-pure elements, B- AB type, C- AB2 type, etc.*
Strukturbericht notation A13
13 is the number in the list.
Pearson symbol cP20 ‘c’ is for cubic, P for primitive, 20 atoms in UC

Pearson symbol: c  cubic, P  simple lattice (not to be confused with primitive unit cell), 20
atoms in unit cell (here they are all Mn, but could be different in other structures).
Mn
Note: In reality the crystal does not have a ‘true’ 4-fold

Point group
P 41 32 ���� � 432
* More details in the next page
 Strukturbericht notation
Strukturbericht
Crystal Type
Designation
A Elements

B AB Compounds

C AB2 or A2B Compounds

D AmBn compounds

E,F,G,H…K More complex compounds e.g. ternary

L Alloys (metallic + intermetallic)

O Organic Compounds

S Silicates
* The number following the letter gives the sequential order of the discovery of the particular structure type. Examples,
A2 structure refers to BCC and B2 refers to an ordered AB compound with B atoms on cell vertices and A atoms on the
B.C. Site.
In some cases, there is more than one derivative of an elemental structure within crystal type (denoted by subscript).
Example, two derivative of FCC (A1) structure are the L1 0 and L12.
 For the crystal below (Fig.1): (i) mark the lattice points, (ii) show the motif, (iii) overlay the
Solved
Example symmetry operators, (iv) mark a primitive & conventional unit cell, (v) write the space group
and point group.

(ii) (i)

Motif

(v) Space group: p4mm

Fig.1 Point group: 4mm

(iii)
(iv)
 For the crystal below (Fig.1): (i) mark the lattice points, (ii) show the motif, (iii) overlay the
Solved
Example symmetry operators, (iv) mark a primitive & conventional unit cell, (v) write the space group
and point group.
(ii)

Motif

(v) Space group: c2mm

Fig.1 Point group: 2mm

Two different ways of associating

the motif with the lattice (i)

(iii)
(iv)
Funda Check How do we chose a motif to be associated with a lattice point?

 As we have noted, there is no unique choice. Two choices of the motif for the square crystal
(patch of the crystal shown in Fig.1) are as below are shown in Fig.2 and Fig.3.

The underlying
square lattice

Fig.1: patch of a Fig.2 Fig.3

square crystal
 For the crystal below, the motif consists of 4 yellow and 4 purple circles. There are many
ways of choosing the motif (i.e. the configuration of 4Y and 4P circles) to be associated with a given lattice
point (as shown).

Lattice point to which the motif is associated

Note that the “net content of the motif is the same”, irrespective of how you
Funda Check  Can 1D crystals be two-dimensional (2D) or 3D?
 Can 2D crystals be 3D?
 The dimension of the crystallinity (sometimes!) has to be decoupled with the dimension of
the periodicity.
 Based on the dimension of periodicity, we classify crystals as 1D, 2D or 3D.
Correspondingly, the underlying lattices are 1D, 2D or 3D.
 A 1D or 2D lattice may be decorated with a 3D motif, thus making the body/material 3D.
 As an extreme example an amorphous 2D/3D layer may be repeated in 1D to get a 1D
crystal. In the 2D plane the ‘atomic’ structure is amorphous; however, the ‘crystal’ has 1D
periodicity.

Amorphous layer

Direction of periodicity