Important crystal structures:

Perovskite structure

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A. Structures derived from cubic close packed

1. NaCl- rock salt
2. CaF2 fluorite/Na2O- antifluorite
3. diamond
4. ZnS- blende
B. Structures derived from hexagonal close packed
1. NiAs nickel arsenide
2. ZnS wurtzite
3. CdI2 cadmium iodide
4. CdCl2 cadmium chloride
C. Non close packed structures
1. CsCl cesium chloride
2. MoS2 - molybdenite
D. Metal oxide structures
1. TiO2- rutile
2. ReO3 rhenium trioxide
3. CaTiO3 perovskite
4. MgAlO4 - Spinel
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Perovskites: ABO3
http://en.wikipedia.org/wiki/File:Perovskite_mineral.jpg

CaTiO3

CaTiO3 mineral was discovered in the Ural mountains (Rusia) in 1839

and is named after Russian mineralogist L.A. Perovski (17921856)
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Perovskite: SrTiO3

Ti at (0, 0, 0);

Corner shared TiO6 Oh

Face shared SrO12 cuboctahedra

Sr at (1/2, 1/2, 1/2)

3O at (, 0, 0),(0, , 0) and (0, 0, )
Ti-O-Ti linear arrangement
0, 1,

0, 1
0, 1,

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0, 1

ABO3
A: 12-coordinate by O (cuboctahedral)
B: 6-coordinate by O (octahedral)
(A fills the vacant centered cubic site in
ReO3)
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Elements found in the perovskite structure

ABO3 - two compositional variables, A and B

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Perovskite - an Inorganic Chameleon

CaTiO3 - dielectric

NaxWO3 - mixed conductor;

electrochromic

BaTiO3 - ferroelectric

SrCeO3 - H - protonic
conductor

Pb(Mg1/3Nb2/3)O3 - relaxor
ferroelectric
Pb(Zr1-xTix)O3 - piezoelectric
(Ba1-xLax)TiO3 - semiconductor
(Y1/3Ba2/3)CuO3-x superconductor
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RECoO3-x - mixed conductor

(Li0.5-3xLa0.5+x)TiO3 - lithium ion

conductor
LaMnO3-x - Giant magnetoresistance

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Close Packed??
Not traditional close packing - mixed cation (A) and anion

SrTiO3

AO3 (SrO3) c.c.p. layers

West book

ideal Perovskite: the cubic cell axis (a) can be related to the ionic radii

a 2rB rO

2rA rO
; rA + rO=2(rB + rO)
2

Examples: NaNbO3 , BaTiO3 , CaZrO3 , YAlO3 , KMgF3

Many undergo small distortions due to size effects and electronic configuration of the B ion
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Size effects in perovskites (ABO3)

t

rA rO "tolerance factor "

2 rB rO

0.8 < t < 1.0 perovskite structure;

t > 1, B ion requires a smaller site;
t < 0.8, the distorted perovskite structure is no longer stable and A ion needs a smaller

0.8

site

0.89
orthorhombic
(GdFeO3)

GdFeO3 (t=0.81)
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1.0
cubic
(SrTiO3)

SrTiO3
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hexagonal
(BaNiO3)

BaNiO3 (t=1.13)

perovskite structure: great stability

allowed variation in the tolerance factor (t) and the subsequent distortions with
the preservation of the basic framework
A and B sites are relatively insensitive to charge distributions:
ex: various valence combinations for A and B cations
1 : 5 NaTaO3;
2 : 4 SrTiO3
3 : 3 LaMnO3
The structure can withstand considerable departures from ideal stoichiometry:
ex: O2- deficiency: La0.5Sr0.5TiO2.5 (50% oxygen deficient LaTiO3 )
CaFeO2.5 (the product of CaO and Fe2O3 in air)
A deficiency: La1/3TaO3; La1/3NbO3;
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d0 transition metals in perovskite structure

Mn+

O2-

O1
Nb

LUMO or
Conduction
Band (CB)

O2
O3

HOMO or
Valence Band (VB)

Out of center distortion

Schematic electronic structure of an undistorted d0 MO6

Small gap between HOMO and LUMO allows for symmetry distortion

This distortion is called Jahn-Teller effect of the second order

The distortion is favored because it stabilizes the HOMO, while destabilizing the LUMO
Bhuvanesh, N. S. P. and Gopalakrishnan, J.; J. Mater. Chem., 1997, 7(12), 22972306
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Jahn-Teller of the second order

The 2nd order JT distortion reduces the symmetry and widens the band gap

The stabilization of HOMO disappears when electrons start filling the band
i.e. for a d1 ion - ReO3 is cubic
1. Octahedrally coordinated high valent d0 cations (i.e. Ti4+, Nb5+, W6+, Mo6+).
BaTiO3, KNbO3 (favored as the HOMO-LUMO splitting decreases - covalency
of the M-O bonds increases)

2. Cations containing filled valence s shells (Sn2+, Sb3+, Pb2+, Bi3+)

Red PbO, SnO, Bi4Ti3O12, Ba3Bi2TeO9 (2nd order JT distortion leads to
development of a stereoactive electron-lone pair)
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BaTiO3
(1) At temp. >120C : cubic perovskite structure
(a=4.018)
(2) At temp.< 120C : tetragonal structure (a=3.997,
c=4.031 )
Views on the [100] direction = a axis
(1)

(2)

the tetragonal distortion leads to

an off-centre displacement of Ti4+
and the dipoles are pointing along c
axis

cubic

tetragonal

tetragonal BaTiO3 is ferroelectric

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Polarization due to out of center displacement of d0 ions

O1
Nb

Ti in (b)

O2

0.1 0.2

Ti in (a)

O3
(a) Ti position in cubic
Oh coordiantion

(b) Ti displacement

Displacement by 5-10% Ti-O bond

length creates a net dipole moment

The ordering of the displaced ions in the perovskite structure depends on:

1. The valence requirements of anions

2. Cation-cation repulsions

An applied electric field can reverse the dipole orientations the structure is polarisable
Random dipole orientations = paraelectric
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Aligned dipole orientation
= ferroelectric

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Properties of d0 transition metals perovskites

BaTiO3-first piezoelectric material discovered
SrTiO3 : Insulator, normal dielectric

BaTiO3 : Ferroelectric (Tc ~ 130C)

PbTiO3 : Ferroelectric (Tc ~ 490C)
KNbO3 : Ferroelectric (Tc ~ x)
KTaO3 : Insulator, normal dielectric

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SrTiO3

vs.

BaTiO3
rBa2+=1.35

rSr2+=1.13

Square pyramidal
coordination (TiO5)

Sr2+

ion is a good fit (d(Ti-O)=1.949),

(SrTiO3 is close to a ferroelectric instability)
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Ba2+ ion stretches the octahedra (d(TiO)2 ) this lowers the energy of LUMO
2nd order Jahn-Teller distortion

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KNbO3

vs.

Ferroelectric

KTaO3
Normal dielectric

Similar bonds and behavior

like in BaTiO3

Ta 5d orbitals are more electropositive and have a larger spatial extent

than Nb 4d orbitals (greater spatial overlap with O 2p), both effects
raise the energy of the t2g LUMO no Jahn-Teller distortion in KTaO3
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Applications of ferroelectrics
For practical applications, the ferroelectric transition should be close
to room temperature
BaTiO3-used as capacitor (storing electric charge) with large
capacitance
The most important piezoelectric is PZT (PbZrO3 + PbTiO3)- used for

sensors, capacitors, actuators and ferroelectric RAM chips

PZT = Pb[ZrxTi1-x]O3 best for x0.5

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3dn transition metals in perovskites

Compound

Electrical Property

Magnetic Property

SrTiO3 (d0)

Insulating

Diamagnetic

SrVO3 (d1)

Metallic

Pauli paramagnetism

SrCrO3 (d2)

Metallic

Pauli paramagnetism

CaMnO3 (d3)

Semiconductor

Antiferromagnetic

LaMnO3-(d3)

Colossal magnetoresistance

Antiferromagnetic

SrFeO3 (d4)

Metallic

Spiral antiferromagnetic

Unpaired electrons in the d shell leads to magnetic interactions through the oxygen
p orbitals
Dramatic change in resistivity in an applied magnetic field gives rise to colossal

magnetoresistance
Pauli paramagnetism is the paramagnetism induced by the excited conduction
electrons
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Magnetism in perovskites
There are two interaction mechanisms :
1. superexchange that leads to antiparallel spin alignment

2. double exchange that leads to parallel spin alignment

(2) Double exchange

(1) Superexchange
eg
d-orbital (M)

p-orbital (X) d-orbital (M)

t2g
Mn4+ (d3)

Mn3+ (d4)

Mn3+ (d4)

Antiparallel or Antiferromagnetic

Mn4+ (d3)
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O2-

O2-

Mn4+ (d3)

Mn3+ (d4)

Parallel or Ferromagnetic

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Layered perovskites
Dion-Jacobson,
A[An-1BnRbLaNb
O3n+1]2 O7

Ruddlesden-Popper,
A2[An-1BnO3n+1]
(AO)(ABO3)n

Aurivillius,
(Bi2O2)[An-1MnO3n+1]

NbO6
La
NbO6
Rb
NbO6
La

AO Rock
salt
layers

Bi2O2
(fluorite
like
layer)

NbO6

suitable systems for investigation the two-dimensional physical properties

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Bi4Ti3O12=(Bi2O2)Bi2Ti3O10

Bi3TiNbO7=(Bi2O2)BiTiNbO7
n=2

n=3

Bi2O2
(fluorite
like
layer)

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 Ruddlesden-Popper (R.P.) phases of Ruthenium: (AO)n+1(RuO2)n:

1. Ca3Ru2O7 (n=2): Mott Hubbard insulator

2. CaRuO3 (n=): paramagnet (becomes
ferromagnetic upon chemical doping)
3. SrRuO3 (n=): ferromagnetic
4. Sr3Ru2O7 (n=2): metamagnet
5. Sr2RuO4 (n=1): superconducting at 1 K

Sr2RuO4
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La2CuO4
It may be viewed as if constructed from an ABAB... arrangement of Perovskite cells
Also known as an intergrowth structures

A
The transparent atoms are missing

Sheets of elongated CuO6

Oh sharing only corners
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Doped La2-xSrxCuO4 {La2-xSrxCuO4 } was the first (1986)

High-Tc Superconducting Oxide (Tc ~ 40 K) for which
Bednorz & Mller were awarded a Nobel Prize

The first of the High Tc superconductors discovered,

La1.85Sr0.15CuO4, has the same basic crystal structure as Sr2RuO4, with
some subtle but important differences due to the difference in d
orbital occupancy.

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Perovskite type superconductors: YBa2Cu3O7-x

(superconducts over 77 K (Boiling point of N2)

2 out of 6 O-Positions in
the structure are
unoccupied
Cu-Atom coordination:
Perovskit
CaTiO3

1/3 square-planar
2/3 square-pyramidal

Triple unit cell

YBa2Cu3O7-x
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1-2-3 Superconductors
YBa2Cu3O7-x ( x < 0.1): Tc = 93K
CuO
chains

O(1)

Ba

O(2)

CuO2
planes O(3)
O(4)

Ba

2 out of 6 O-Positions of the

Perovskites are unoccupied

YBa2Cu3O7-x (x 0.07 optimum for

highest Tc)

Perovskit 3 unit cells (A=Ba, A=Y, B=Cu)

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YBa2Cu3O7-

= 0.08 Tc=93K
> 0.56 not superconductor (tetragonal structure)

400 C , O
2 orthorhombic
tetragonal

O (1) site almost missing

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CuO2 planes are the SC layers

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YBa2Cu3O7-x: intergrowth structure

Layers stacked in the sequence:
Cu(1)OBaOCu(2)O2YCu(2)O2BaOCu(1)O
Cu(1)O

UNIQUE SEQUENCE OF LAYERS:

BaO

1) Charge reservoirs layers (insulating), such

Cu(2)O2
Y
Cu(2)O2
BaO
Cu(1)O

as [Cu(1)O]
2) Spacing layers: such as [BaO]-2 layers

3) Separating layers: such as [Y]-1 layer

4)Superconducting layers [Cu(2)O2]-2 layers
1212

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CuBa2YCu2O7 (YBa2Cu3O7)

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Naming Scheme of the cuprates

1223

TlBa2Ca2Cu3O9

Annu. Rev. Mater. Sci. 1997. 27:3567

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I . the number of insulating layers between adjacent

conducting blocks
II. the number of spacing layers between identical CuO2
blocks
III. the number of layers that separate adjacent CuO2
planes within the conducting block
IV. the number of CuO2 planes within a conducting block.

0201

(La1-xSrx)2CuO4

1212

HgBa2CaCu2O6

1212

CuBa2YCu2O7 (Usually written YBa2Cu3O7)

1223

TlBa2Ca2Cu3O9

2201

Bi2Sr2CuO6

2234

Tl2Ba2Ca3Cu4O12

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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

Ba La - very slight increase?

Cu transition metals - decrease in Tc

Cu Au - very slight increase?

Generally detrimental!
Skakle, .Mat. Sci. Eng: R: Reports, 23 1-40 (1998)

It is believed that the superconductivity depends on the number of

CuO2 planes per unit cell
YBa2Cu3O7 (1212): 2 CuO2 layers Tc=93K
Bi2Sr2Ca2Cu3O10 (Bi-2223): 3 CuO2 layers Tc=110K

Tl2Ba2Ca2Cu3O10 (Tl-2223): 3 CuO2 layers Tc=125K

HgBa2Ca2Cu3O8 (Hg-1223): 3 CuO2 layers Tc=134K
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Composition

Physical Property

Possible or present application

CaTiO3

Dielectric

Microwave applications

BaTiO3

Ferroelectric

Non volatile computer memories

PbZr1-xTixO3

Piezoelectric

Sensors

(Pb,La)(Zr,Ti)O3

Optical

Electro-optical modulator

Ba1-xLaxTiO3

Semiconductor

Semiconductor applications

GdFeO3, LaMnO3

Magnetic

Magnetic memories, ferromagnetism

Y0.33Ba0.67CuO3-x

Superconductor

Magnetic detectors

LnCoO3-x

Mixed ionic and electronic

Gas diffusion membranes

conductor
BaInO2.5

Ionic conductor

Electrolyte in solid oxide fuel cells

AMnO3-x

Giant magneto resistance

Read heads in hard disks

YAlO3, KNbO3

Optical

Laser

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