Modification of Insulators.

The electrical properties of electronic insulators can be modified to become

electronic semiconductors or even metals by suitable chemical doping. This is
especially true for transition metal oxides. Why?
Transition metal (TM) cations can exhibit variable oxidation states (OS).
TM

Sc

OS

Ti

Cr

2,3,4 3,4,6

Mn

Fe

Co

Ni

Cu

3,4,5

2-7

2,3,4

2,3,4

2,3, 1, 2,3

Zn
2

Some undergo oxidation of the TM cation, eg NiO Oxygen gain : NiO1+ Ni2+/3+
Some undergo reduction of the TM cation, eg. TiO2 Oxygen loss : TiO2- Ti4+/3+
Mixed valency of TM cation can induce mobile holes or electrons in such solids
Dopants can also act as donors or acceptors.
Two examples :

Li+ doping of NiO (p-type doping)

Li+ for Ni2+ acceptor

La3+ doping of BaTiO3 (n-type doping) La3+ for Ba2+ donor

The d band.
The basic energy level diagram for a TM oxide (TMO) is similar to that of
other ionic compounds, with a VB of oxygen 2p character and a CB of metal
character. However, the lowest metal orbitals are normally the d, rather than s
in the pre-transition elements.
The d orbitals can (in some cases) form a single band, separated from those
of the higher energy s and p orbitals of the TM.
TiO2, V2O5 (d0)
0
For d cations the d band is empty. Insulators case (a)
For some d e- containing compounds we have partially filled d-band.
Metals case (b).
Metal s and p
bands

Ti2O3, VO2 (d1)

Metal d band

Ef

Eg
O 2p VB
Energy
(a)
Insulator, d0 cation

(b)
Metal , d1 cation

La-doped BaTiO3
BaTiO3 is a white, band gap insulator. Eg ~ 3.2 eV. Perovskite (ABO3) structure
La3+ (donor) doping on the Ba2+ site (~ 0.3 at%) turns BaTiO3 into a black
semiconductor. Mechanism?

Ba2+ and La3+ are similar in size so La replaces Ba on the A-site

Ba2+ + Ti4+ La3+ + Ti3+
(Ba1-xLax)TiO3 is, in fact : (Ba1-xLax) (Ti1-x4+Tix3+)O3
do

d1

Note : some d0 transition metal cations can be reduced to d1 cations

eg. V5+ (do) V4+ (d1).

(Ba,La)TiO3, with mixed valence Ti, is a good (n-type) semiconductor.

An example of donor doping or adding electrons.
A donor dopant ion (D) has a higher valence state (n)
than the host ion (H).
In general : D(n+1) + e- Hn

(Here La3+ + e- Ba2+)

Band Picture for insulating and semiconducting BaTiO 3

Ti, 3d-band

Empty CB
Eg

O, 2p-band

Partially filled
3d band
e- e-

eED (La)

Full VB

Pure BaTiO3
(d0) insulator

Semiconducting
(Ba,La)TiO3
Discrete La donor levels
just below the CB
Exhaustion at 300 K
n-type semiconductivity

Aliovalent doping.

Some ions of different charge but similar size that readily substitute for
each other.
Use periodic table trends: nearest neighbours or 'diagonal relationships'
Li+
Na+
Si4+
Zr4+
V5+
La3+

Mg2+
Ca2+
Al3+
Y3+
Mo6+
Ba2+

TM2+

Ca2+

eg. 0.9
eg. 1.16
eg. 0.40
eg. 0.86
eg. 0.68
eg. 1.71

0.86 Ni = 0.83 (CN = 6)

1.14
(CN = 6)
0.53
(CN = 4)
1.04 1.14
(CN = 6)
0.73
(CN = 6)
1.50
(CN = 12)

Bonding trends for compounds.

Compounds within p-block, eg GaAs have high degree of covalent bonding
Oxides with s-block elements, eg SrO have high degree of ionic bonding
Oxides with d-block elements, eg TiO2, (Ba,La)TiO3 Ti2O3 have mixed bonding

Cation size increases

Anions are large

Cation size decreases

Image from http://www.crystalmaker.com/support/tutorials/crystalmaker/resources/SP_Crystal_Radii.jpg

Whether or not the band picture works depends on the:-

Size of the atoms;

Crystal structure;
Type of bonding.

These factors dictate the level of orbital overlap of the atoms and how
the valence electrons are distributed in the solid.

Dielectric Materials

Any non-conducting material - insulators

Complete absence of charge movement under an electric field
A dielectric material is a substance that is a poor conductor of electricity, but an
efficient supporter of electrostatic fields.
Materials may be
ionic: MgO, Al2O3, mica

covalent: CDIAMOND, polythene, pvc

polar covalent: SiO2

We tend to divide non-conductors into two types:

Ones we use as insulators such as polymers or perhaps porcelain
or SiO2 (glass)
Ones we use in electrical circuits in devices such as capacitors
A capacitor is a device used to store charge. The simplest device is two
separated parallel plates. These will not conduct DC current although
will appear to do so for AC

Capacitors

In a DC circuit, charge will build up across two parallel plates so that the
capacitor stores charge. If the capacitor is short circuited then charge will
flow. In reality, when building the charge there is a transient current but it
lasts for a very short time.
- +
C
- +
-

When any material is introduced between two parallel plates of a capacitor, the
total charge stored in the capacitor will change. The change depends on the
ability of the material to polarize under an electric field. The dielectric constant,
or permittivity, , of a material determines the change in charge storage.

For high capacity applications, a high dielectric constant is needed.

Positive plate
++++++++++++++++++
- - - - - - - - - -- - - - - - - - - - - - d

dielectric
++++++++++++++++
--------------------- ---Negative plate

Dielectric can polarise to

produce a surface charge

Plate area A

With a vacuum between the plates, capacitance C is defined by:

Co = oA/d
o, is the permittivity of free space = 8.85 x 10-12 F.m-1

Applying a potential difference between two parallel plates results in the plates
storing a charge qo.
q o = CoV

Placing a dielectric between the plates allows a higher charge, C1 to be

accumulated, giving increased capacitance. The dielectric property of the
= C1/C0
material, , is given by:

0 for vacuum is 8.85 x 10-12 F.m-1

Dielectric constant, , is ratio of permittivity of material to that of a vacuum

and is related to the degree of polarisation that can occur within the
material, ie charge displacement. also known as the relative permittivity

Dielectric strength is voltage at which the insulating properties break down

and current begins to flow. Units are kV.mm-1

For practical use, a good dielectric material should have high dielectric
strength, and low dielectric loss, the energy lost through heating of electrical
energy (in AC)

There is a special class of dielectrics (ferroelectrics) that have very high .

An example is insulating BaTiO3 with ~ 1000 3000.

~ 10 for many oxides, eg Al2O3, and MgO.

Over 1.3 Trillion BaTiO3-based capacitors produced last year!

Typical dielectric values

Material
Vacuum
Air
Water
Paper
Ruby mica
Porcelain
Polythene
Teflon
TiO2
BN
MgO
Glass
Al2O3
Polystyrene

1.00000
1.0054
78
3.5
5.4
6.5
2.3
2.1
100
4.5
9.6
6.9
10.1
2.6

Dielectric strength kVmm-1

0.8
14
100
4
50
60
6
2.4
8 -13
9.75
9.50
19.5-27.3

Applications : Insulators, capacitors, microwave and RF components,

heat sinks, power electronics, microcircuit packaging, plasma arcs etc.