Ordered Structures

Please revise the concept of Sublattices and Subcrystals by clicking here

before proceeding with this topic

MATERIALS SCIENCE
Part of & AALearners
LearnersGuide
Guide
ENGINEERING
AN INTRODUCTORY E-BOOK
Anandh Subramaniam & Kantesh Balani
Materials Science and Engineering (MSE)
Indian Institute of Technology, Kanpur- 208016
Email: anandh@iitk.ac.in, URL: home.iitk.ac.in/~anandh
http://home.iitk.ac.in/~anandh/E-book.htm
 Superlattices and Ordered Structures

Often the term superlattice# and ordered structure is used interchangeably.

The term superlattice implies the superlattice is made up of sublattices.
An ordered structure (e.g. CuZn, B2 structure*) is a superlattice. An ordered structure is a
product of an ordering transformation of an disordered structure (e.g. CuZn BCC
structure*)
But, not all superlattices are ordered structures. E.g. NaCl crystal consists of two
subcrystals (one FCC sublattice occupied by Na+ ions and other FCC sublattice by Cl
ions). So technically NaCl is a superlattice (should have been called a supercrystal!) but
not an ordered structure.

Click here to revise

concepts about
Sublattices &
Subcrystals

Click here to see XRD patterns from ordered structures

* Explained in an upcoming slide.
# Sometimes the term superlattice is used wrongly: e.g. in the case of Ag nanocrystals arranged in a FCC lattice the resulting Nano-crystalline
solid is sometimes wrongly referred to as a superlattice.
Order-Disorder Transformations

One interesting class of alloys are those, which show order-disorder transformations.
Typically the high temperature phase is dis-ordered while the low temperature phase is
ordered (e.g. CuZn system next slide).
Click here to revise
The order can be positional or orientational.
concepts about
In case of positionally ordered structures: Sublattices &
The ordered structure can be considered as a superlattice Subcrystals
The superlattice consists of two or more interpenetrating sub-lattices
with each sublattice being occupied by a specific elements
(further complications include: SL-1 being occupied by A-atoms and SL-2 being occupied by
B & C atoms- with probabilistic occupation of B & C atoms in SL-2, which is disordered).
Order and disorder can be with respect to a physical property like magnetization. E.g. in the
Ferromagnetic phase of Fe, the magnetic moments (spins) are aligned within a domain. On
heating Fe above the Curie temperature the magnetic moments become randomly oriented,
giving rise to the paramagnetic phase.
Even vacancies get ordered in a sublattice. A vacancy in a vacancy sublattice is an atom!!
The disordered phase is truly an amorphous structure and is considered a crystal in
probabilistic occupational sense. [Click here to know more]
 Diagrams not to scale
Positional Order In the order-disorder transformation shown in the figures below
the high temperature phase is disordered and has a BCC lattice, while the low temperature
structure is simple cubic (B2 structure).
In a strict sense this
High T disordered is not a crystal !!

BCC

Probabilistic occupation of each BCC lattice site:

50% by Cu, 50% by Zn

G = H TS 470C

Sublattice-1 (SL-1)

B2
structure
Sublattice-2 (SL-2)

Low T ordered
SC
SL-1 occupied by Cu and SL-2 occupied by Zn. Origin of SL-2 at (, , )
ORDERING
A-B bonds are preferred to AA or BB bonds
e.g. Cu-Zn bonds are preferred compared to Cu-Cu or Zn-Zn bonds
The ordered alloy in the Cu-Zn alloys is an example of an INTERMEDIATE
STRUCTURE that forms in the system with limited solid solubility
The structure of the ordered alloy is different from that of both the component
elements (Cu-FCC, Zn-HCP)
The formation of the ordered structure is accompanied by change in properties.
E.g. in Permalloy ordering leads to reduction in magnetic permeability,
increase in hardness etc. [~Compound]
Complete solid solutions are formed when the ratios of the components of the
alloy (atomic) are whole no.s 1:1, 1:2, 1:3 etc. [CuAu, Cu3Au..]
Ordered solid solutions are (in some sense) in-between solid solutions and
chemical compounds
Degree of order decreases on heating and vanishes on reaching disordering
temperature [ compound]
Off stoichiometry in the ordered structure is accommodated by:
Vacancies in one of the sublattices (structural vacancies)
NiAl with B2 structure Al rich compositions result from vacant Ni sites
Replacement of atom in one sublattice with atoms from other sublattice
NiAl with B2 structure Ni rich compositions result from antisite defects
Let us consider some more ordered structures

NiAl This is similar to CuZn

Lattice: Simple Cubic

Unit cell formula: NiAl Two interpenetrating Simple Cubic

crystals (origin of crystal-1 at (0,0,0)
and origin of crystal-2 at (,,))

SC

Motif: 1Ni + 1Al

NiAl
Lattice parameter(s) a = 2.88
Space Group P 4/m 3 2/m (221)
Strukturbericht notation B2
Pearson symbol cP2
Other examples with this structure CsCl, CuZn
CuAu (I)

Cu

Au

Cu

Lattice: Simple Tetragonal

Au
Motif: 2Au +2Cu
(consistent with stoichiometry) Unit cell formula: Cu2Au2
CuAu
Lattice parameter(s) a = 3.96, c = 3.67
Wyckoff
Space Group P 4/m 2/m 2/m (123) x y z
position
Strukturbericht notation L10
Au1 1a 0 0 0
Pearson symbol tP4 Au2 1c 0.5 0.5 0
Other examples with this structure TiAl Cu 2e 0 0.5 0.5
 Q&A How to understand the CuAu ordered structure in terms of the language of
superlattices?

The crystal is simple (primitive) tetragonal

The formula for the UC is 2Cu + 2Au
we need two sublattices for Au and two sublattices for Cu

Origin for the Cu subcrystal-2

Cu

Origin for the Cu subcrystal-1

Au

Origin for the Au subcrystal-2

Origin for the Au subcrystal-1

All subcrystals are tetragonal (primitive)
Cu3Au

Cu

Au

Lattice: Simple Cubic

Motif: 3Cu +1Au (consistent with stoichiometry)

Cu3Au
Lattice parameter(s) a = 3.75
Space Group P 4/m 3 2/m (221)
Strukturbericht notation L12
Pearson symbol cP4
Other examples with this structure Ni3Al, TiPt3
Ni3Al This is similar to Cu3Au

Ni3Al
Lattice parameter(s) a = 3.56
Space Group P 4/m 3 2/m (221)
Strukturbericht notation L12
Pearson symbol cP4
Other examples with this structure Cu3Au, TiPt3
 Al3Ni [100]
[010]
[001]

Formula for Unit cell: Al12Ni4

Al3Ni Wyckoff Site

x y z Occupancy
position Symmetry
Lattice parameter(s) a = 6.62 , b = 7.47 , c = 4.68
Ni 4c .m. 0.3764 0.25 0.4426 1
Space Group P 21/n 21/m 21/a (Pnma) (62)
Al1 4c .m. 0.0388 0.25 0.6578 1
Strukturbericht notation DO20
Al2 8d 1 0.1834 0.0689 0.1656 1
Pearson symbol oP16
Other examples Fe3C
Fe3Al

Fe

Al
Fe2 (,,)

Fe1 (,,0)
Fe1 (0,0,0)

Dark blue: Fe at corners

Lighter blue: Fe at face centres
V. Light Blue: Fe at (,,)
Fe: Vertex-1, FC-3, (,,)-8 12
Al: Edge-3, BC-1 4
Unit cell formula: Fe12Al4

Fe3Al Wyckoff
Lattice parameter(s) a = 5.792 position
Space Group F 4/m 3 2/m (225) Fe1 4a 0 0 0
Strukturbericht notation DO3 Fe2 8c 0.25 0.25 0.25
Pearson symbol cF16 Al 4b 0.5 0 0

Other examples with this structure Fe3Bi

 Fe

Al
Fe

Motif: 3Fe +1Al (consistent with stoichiometry)

Lattice: Face Centred Cubic

Assignment:
(i) try to put the motif at each lattice point and obtain the entire crystal
(ii) Chose alternate motifs to accomplish the same task
 Fe3Al
More views

Fe

Al

[100]
 Fe3Al
More views

Fe1 and Fe2 have

Fe2 (,,)
different environments

Fe1 (,,0)

Fe1 (0,0,0)

Fe1 (0,0,0)
Cube of Fe

Tetrahedron of Fe
Tetrahedron of Al

Fe2 (,,)

Fe1 (,,0)
Spin Ordering
In Ferromagnets, Ferrimagnets and Antiferromagnets, spin (magnetization vector) is ordered.
A schematic of the possible orderings is shown in the figure below (more complicated orderings
are also possible!).
We shall consider Antiferromagnetism as an example to show the formation of superlattices
(ordered structures).
Above the Curie or Nel temperature the spin structure will become disordered and state would
be paramagnetic
Antiferromagnetic ordering

MnF2 is antiferromagnetic below 67K (TN)

(b)
(a)

MnF2
Wyckoff Site
Lattice parameter(s) a = 4.87, b = 4.87, c = 3.31 () x y z Occupancy
position Symmetry
Space Group P42/mnm (136) Mn 2a m.2m 0 0 0 1
Pearson symbol tP6 F 4f m.mm 0.305 0.305 0 1
Other examples with this structure TiO2
 MnO Disordered
Wyckoff Site
Lattice parameter(s) a = 4.4 () x y z Occupancy
position Symmetry
Space Group Fm-3m (225)
Mn 4a m-3m 0 0 0 1
Pearson symbol cF8
O 4b m-3m 0.5 0.5 0.5 1
Other examples with this structure NaCl
 Anti ferromagnetic MnO, TN =122K
Perfect order not obtained even at low temperatures
Rhombohedral angle changes with lowering of temperature
Rhombohedral, a = 8.873, = 9026 at 4.2K
even above Nel temperature order persists in domains about 5nm in size
 MnAu2

Nice example of antiferromagnetic ordering where the spins are not anti-parallel.
TN = 363K
Helical spin structure
Metamagnetic behaviour- field induced transition to ferromagnetism

MnAu2
Wyckoff Site
Lattice parameter(s) a =3.37, b = 3.37, c = 8.79 x y z Occupancy
position Symmetry
Space Group I4/mmm (139) Mn 2a 4/mmm 0 0 0 1
Pearson symbol tI6 Au 4e 4mm 0 0 0.335 1
Other examples with this structure MoSi2
Disordered Cu3Au

Disordered Ordered
- Ni3Al, FCC L12 (AuCu3-I

Ordered
Superlattice lines
Funda Check How to understand the statement that: on ordering the symmetry decreases?

The ordered structure has lower symmetry.

This can be: reduction in point group symmetry or increase in the length of the
shortest lattice translation vector. The reduction in point group symmetry could be due to
ordering of a physical property (e.g. magnetic moment from electron spins).
50% chance of
occupation by A or B

Cubic (P4/m 3 2/m)

becomes Tetragonal
(P 4/m 2/m 2/m)
Cu
bi
be tim c (o
co e f s
m av pi
es er ns
Te age ar
tra d) e
50% chance of go
occupation by A or B na
l

Reduction in the length of the

shortest repeat periodicity
(vector) on ordering

Shortest vector: [111]

Shortest vector: [100]
length = 3/2
length = 1