Objectives

By the end of this section you should:

be able to identify and draw the perovskite
structure
understand how the perovskite structure can
become polarisable
know the basic properties of barium titanate
know the basic properties of YBa2Cu3O7
understand how properties are modified by
appropriate substitutions

Perovskite an Inorganic Chameleon

ABX3 - three compositional variables, A, B and X
CaTiO3 - dielectric
BaTiO3 - ferroelectric
Pb(Mg1/3Nb2/3)O3 - relaxor
ferroelectric
Pb(Zr1-xTix)O3 - piezoelectric
(Ba1-xLax)TiO3 - semiconductor
(Y1/3Ba2/3)CuO3-x - superconductor

NaxWO3 - mixed conductor;

electrochromic
SrCeO3 - H - protonic conductor
RECoO3-x - mixed conductor
(Li0.5-3xLa0.5+x)TiO3 - lithium ion
conductor
LaMnO3-x - Giant magnetoresistance

Perovskite Structure
ABO3

e.g. KNbO3
SrTiO3
LaMnO3
SrTiO3 cubic, a = 3.91

In SrTiO3, Ti-O = a/2 = 1.955

Sr-O = a2/2 = 2.765
CN of A=12, CN of B=6

OR

Close Packed??
Not traditional close packing mixed cation/anion

AX3 ccp layers.

B in 1/4 of octahedral sites

In SrTiO3, Ti-O ~ 1.95

a typical bond length for Ti-O;
stable as a cubic structure
larger

In BaTiO3, Ti-O is stretched, > 2.0

Too long for a stable structure.
Ti displaces off its central position
towards one oxygen
square pyramidal coordination

This creates a net dipole moment :

Displacement by 5-10% Ti-O bond length

Random dipole orientations

paraelectric

Aligned dipole orientations

ferroelectric

Under an applied electric field, dipole orientations can be

reversed, i.e. the structure is polarisable
Dipoles tend to be frozen in at room temperature; as increase
temperature, thermal vibrations increase the polarisability

Define the permittivity or dielectric constant of a

material by:

Q

Q vac

H2O is a polar liquid; ~ 80

Typical ionic solids; ~ 10
Air; ~ 1
BaTiO3 :-

Below 120C, BaTiO3 is ferroelectric with aligned

dipoles.
Residual dipole disorder gives ~200-1000
At ~127C, tetragonal cubic phase transition.
Dipoles randomise and increases to ~5,000-10,000

For capacitor applications, need to increase capacitance [energy

stored/mass or volume] by increasing Q and thus increasing
How to do this? BaTiO3 is very good at 120C but want high at
room temperature!
1) Partial substitution of Ba by a smaller M2+ ion - Sr2+ ; unit cell
volume decreases and the phase transition temperature decreases

2) Disrupt dipoles by modifying B-site ions

3 Ti4+ Mg2+ + 2 Nb5+
Ti-O ~ 1.96 ;

Nb-O ~2.02, Mg-O ~ 2.12

NbO6 octahedra may be polar; MgO6 octahedra are not.

Pb(Mg1/3Nb2/3)O3
PMN
a relaxor ferroelectric

Superconductors
YBa2Cu3O7-
Perovskite?
(YBa2) Cu3 O9-x
Oxygen Deficient
Triple Perovskite
Crosses mark
absent oxygens

Properties
YBa2Cu3O7
superconductor
- resistance lost completely
at temperature Tc
YBa2Cu3O6
semiconductor
- oxygen lost from base of
unit cell

Properties
YBa2Cu3O7
superconductor
- perfect diamagnet (excludes a
magnetic field)
Magnetic levitation

http://www.youtube.com/watch?v=hksy_4Zmh80
http://www.realboring.com/floating-magnet/ Alert!

Properties
YBa2Cu3O7-

As increases:
1) Tc decreases
2) symmetry changes
from orthorhombic to
tetragonal
(oxygen atoms
rearrange in base)

O = orthorhombic, T = tetragonal

Changing Properties?
Can substitute many elements into YBa2Cu3O7
structure:
Y lanthanides - no change in Tc
Y other elements - decrease in Tc
Ba Sr, Ca - decrease in Tc
Cu transition metals - decrease in Tc
Cu Au - very slight increase?
Ba La - very slight increase?
Generally detrimental!
Skakle, .Mat. Sci. Eng: R: Reports, 23 1-40 (1998)

Summary
The perovskite structure, typified by the formula
ABX3, is a highly adaptable structure
In BaTiO3, Ti is displaced from its site to create a
dipole - alignment of this dipole leads to interesting
electrical properties
BaTiO3 undergoes a paraelectric-ferroelectric
transition at 120C. This may be modified by
chemical substitutions.
The superconductor YBa2Cu3O7- (YBCO) can be
described as an oxygen deficient perovskite
The properties of YBCO change with the crystal
structure.