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Module 1 SPINEL

The document discusses the spinel and perovskite crystal structures. The spinel structure has the formula (A2+)(B3+)2O4 and can exist in normal or inverse forms depending on how the cations occupy tetrahedral and octahedral sites. The perovskite structure has the formula ABO3 and consists of corner-sharing BO6 octahedra with the A cation sitting in the gaps. The tolerance factor describes ideal cubic symmetry in perovskites. Both structures are important for materials like ferrites and titanates that find technological applications.

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Dharmendra Kumar Srivastava
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625 views5 pages

Module 1 SPINEL

The document discusses the spinel and perovskite crystal structures. The spinel structure has the formula (A2+)(B3+)2O4 and can exist in normal or inverse forms depending on how the cations occupy tetrahedral and octahedral sites. The perovskite structure has the formula ABO3 and consists of corner-sharing BO6 octahedra with the A cation sitting in the gaps. The tolerance factor describes ideal cubic symmetry in perovskites. Both structures are important for materials like ferrites and titanates that find technological applications.

Uploaded by

Dharmendra Kumar Srivastava
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© © All Rights Reserved
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SOLID STATE LAST LECTURE Dr. D.K.

Srivastava
Compounds based on FCC Packing of Ions

Spinel Structure

 Formulae – (A2+)(B3+)2O4 or AB2O4 or AO.B2O3


 FCC Packing of anions
 Partial occupancy of both tetrahedral and octahedral sites i.e.1/8th of tetrahedral and ½
of the octahedral sites are occupied.
 A spinel unit-cell is made up of eight FCC cells made by oxygen ions in the
configuration 2×2×2, so it is a big structure consisting of 32 oxygen atoms, 8 A atoms
and 16 B atoms.
 Depending on how cations occupy different interstices, spinel structure can be
Normal or Inverse.

Normal Spinel
 Chemical formula: (A2+)(B3+)O4
 Examples are many aluminates such as MgAl2O4, FeAl2O4, CoAl2O4 and a few
ferrites such as ZnFe2O4 and CdFe2O4.
 In this structure, all the A2+ ions occupy the tetrahedral sites and all the B3+ ions
occupy the octahedral sites.
 Apply bond strength rule to verify the stoichiometry
 Cations: - A2+ - 2⁄4 ; B3+ - 3⁄6
Oxygen valence = (2⁄4x1)+ (3⁄6x3) = 2

Figure Schematic of spinel structure

Inverse Spinel B(AB)O4

 Chemical formula: (A2+)(B3+)2O4 but can be more conveniently written as B(AB)O4.


 Most ferrite follow this structure such as Fe3O4 (or FeO.Fe2O3), NiFe2O4, CoFe2O4
etc.
 In this structure, ½ of the B3+ ions occupy the tetrahedral sites and remaining ½ B3+
and all A2+ ions occupy the octahedral sites (now you can hopefully make sense of the
formula in the previous line).

Dr. D. K. Srivastava

Other Cubic Structures


There are a few structures, which appear as if they are based on cubic closed packing of
anions. However the actual structure is rather different and many of these structures are
merely based on the cubic packing of anions. Here, we discuss the perovskite structure based
on ABO3 structure, CsCl structure and ReO3 structure.

Perovskite (ABO3) Structure

 ABO3 type compounds


 Examples are many titanates like BaTiO3, SrTiO3, PbTiO3 etc. which happen to be
technologically very useful compounds as we will see in later modules.
 In ABO3 structured compounds, A ion is twelve fold coordinated by oxygen (like a
dodecahedra) and B ion is octahedrally coordinated by oxygen ions.
 Oxygen atoms form an FCC-like (not FCC) cell with atoms missing from the corners
which are occupied by A atoms.
 Bond strength check:
Cation: Ba: 2⁄12 = 1⁄6 and Ti: 4⁄6 = 2⁄3
Oxygen valence = 1⁄6 x Coordination number by Ba + 2⁄3 x coordination number by Ti
.

Figure 1.31 Perovskite structure


Figure 1.32 Polyhedra model of perovskite structure

 Lattice type: Primitive Cubic (NOT FCC!)


 Motif: A ion - 0 0 0, B ion – ½ ½ ½, O ion - ½ ½ 0, 0 ½ ½, ½ 0 ½
 One Formula unit per unit cell
 Coordination
o B cation is surrounded by oxygen octahedra which share corners.
o A cation is surrounded by oxygen dodecahedra which touch faces of
octahedra.
 An important parameters about perovskites is the their “Tolerance Factor (t)” which is
defined as

 This is derived from the geometry of a cube in which the atoms are of such sizes that
they touch each other and hence, the face diagonal of the unit cell would be times
the unit-cell length, as result t = 1 for a perfect cubic perovskite

 However, due to variations in ionic radii of various ions, many perovskites show
deviations from t = 1 and may not even have a cubic structure. Deviations from t = 1
signify the level of lattice distortion.
 For example, BaTiO3 has cubic structure only above ~120°C while it is tetragonal at
room temperature and further adopts orthorhombic and rhombohedral structure if
cooled below RT.
 Perovskites can also have various combinations of ionic valence such as
o e.g. A2+B4+O4 , BaTiO3, PbTiO3, CaTiO3, SrTiO3 etc.
o e.g. A3+B3+O4 , LaAlO3, LaGaO3, BiFeO3 etc.
o Mixed Perovskites:
 A2+(B2+1/3B5+2/3)O3 eg. Pb(Mg1/3Nb2/3)O3
 A2+(B3+1/2B5+1/2)O3 eg. Pb(Sc1/2Ta1/2)O3

Dr. D. K. Srivastava

ReO3 Structure
 Stoichiometry : MX3
 Lattice type: Primitive cubic
 Atomic Positions: M- 0 0 0; X - ½ 0 0, 0 ½ 0, 0 0 ½
 Coordination Numbers
M CN = 6 Octahedral coordination
X CN = 2 Linear coordination
 Can be visualized as perovskite ABO3 structure with empty B-sites
 Representative Oxides
o ReO3, UO3, WO3
 Used for gas sensing and electrochromic applications

Figure 1.33 ReO3 structure and polyhedra model

Other Cubic Structures

CsCl Structure

 MX type compounds, parent compound being CsCl.


 Examples: Halides such as CSCl, AgI, AgBr etc.
 Radius ratio governs cubic co-ordination of both cations and anions.
 Lattice type: Primitive cubic lattice.
 Motif: Anions (X): 0 0 0, Cations (M): ½ ½ ½
 One formula unit per unit cell.
Figure 1.34 (a) CsCl structure (b) Ball-stick model

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