SOLID STATE

1.SPINELS AND INVERSE SPINELS

2. PEROVSKITES
BY
SHOBANA.N.S
QUEEN MARY’S COLLEGE
Spinel

• Spinels generally refer to metal oxides having

general formula AB2X4

• The spinel that is most popularly known is

MgAl2O4
AB2X4

 Where
AII = a divalent cation like Mg, Cr, Mn, Fe, Co,
Ni, Cu, Zn, Cd, Sn
BIII = a trivalent cation like Al, Ga, In, Ti, V, Cr, Mn,
Fe, Fe, Co, Ni
X = O, S, Se etc.
Crystal Structure of Spinels

Normal spinel structures are usually cubic

close-packed oxides with one
octahedral and two tetrahedral sites per
formula unit.

B3+ ions occupy half the octahedral

holes, while A2+ ions occupy one-eighth
of the tetrahedral holes.
Examples In4SnS8 and MgAl2O4

OTHER EXAMPLES:
Mn3O4, ZnFe2O4,
FeCr2O4
(chromite) etc
Their crystalline
structure is identical
to natural spinel, So
surprisingly, they can
mimic the blues of
aquamarine, zircon
or blue topaz, and
blue sapphire.
ZnCr 2 O 4

ZnCr 2 O 4

ZnCr 2 O 4

Presence of Cations

 Let us consider the case of ZnCr2O4

Zn +2 d-10 ion with CFSE = 0 and thus, there will

be no effect on Oh holes.

Cr +3 d-3 ion with CFSE = -8Dq and hence this

cations will occupy the Oh holes.

Hence higher the CFSC value, greater is its tendency to

occupy octahedral hole.
 Applications

 Due to greater refractive index, spinels are generally used as Gemstones. Black
These spinel gemstones are considered very rare and precious. Prince’s
ruby
Timur Ruby
398.72-
carat

Catherine the
Great’s ruby
Samarian Spinel

• The fourth largest Spinel.

• It is a 500-carat spinel
gemstone.
Other Applications

 Spinels are generally used in TV and Phone screens.

 Super magnets

 Used as superconducting magnet in MRI and NMR

Inverse Spinel

This picture compares the

crystal structure of inverse
Spinels with spinels.
STRUCTURAL ARRANGEMENT

 Inverse Spinels usually have alternate arrangement.

 The AII ions occupy the octahedral voids, whereas half of BIII ions occupy
the tetrahedral voids

 It can be represented as: (BIII)tet(AIIBIII)octO4

 Most ferrite follow this structure such as

Fe3O4 (or FeO.Fe2O3), NiFe2O4, CoFe2O4 etc
MAGNETIC PROPERTY
CONCLUSION
APPLICATION

 Iron oxide nanoparticles:

Iron oxide nanoparticles are iron oxide particles with diameters
between about 1 and 100 nanometers.

The two main forms are magnetite (Fe3O4) and its

oxidized form maghemite (γ-Fe2O3).

They have attracted extensive interest due to their super

paramagnetic properties
Perovskites

 They are ternary oxides of general formula ABX3.

 where the anion X can be O, N, or F.

 The A ions are typically large ions such as Sr2+, Ba2+,

Rb+, or a lanthanide 3+ ion

 The B ions are smaller transition metal ions such

as Ti4+, Nb5+, Ru4+, etc

A,B,X- White,
Blue and Red
Examples

 Examples are many titanates like BaTiO3, SrTiO3, PbTiO3 etc. which happen
to be technologically very useful compounds
TYPES OF PEROVSKITES

Perovskites can also have various combinations of ionic valence such as

• e.g. A2+B4+O4 , BaTiO3, PbTiO3, CaTiO3, SrTiO3 etc.

• e.g. A3+B3+O4 , LaAlO3, LaGaO3, BiFeO3 etc.

Mixed Perovskites:

• A2+(B2+1/3B5+2/3)O3 e.g.. Pb(Mg1/3Nb2/3)O3

• A2+(B3+1/2B5+1/2)O3 e.g.. Pb(Sc1/2Ta1/2)O3

APPLICATION

 Perovskites solar cells:

A perovskite solar cell is a type of solar cell which includes a perovskite
absorber.
This act as the light-harvesting active layer, which produces electricity from
sunlight.
Perovskite absorber materials are extremely cheap to produce and
simple to manufacture
Lasers

 In 2014 researchers demonstrated that perovskite can generate laser light

 Methyl ammonium lead iodide perovskite (CH3NH3PbI3-xClx)

cells fashioned into optically pumped
vertical-cavity surface-emitting lasers (VCSELs) convert
visible pump light to near-IR laser light with a 70% efficiency.[
Photo electrolysis

 Water electrolysis at 12.3% efficiency in a highly efficient and low-cost

water-splitting cell using perovskite photovoltaics
THANK YOU!!!