Lecture 8. 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 Ti Cr V Mn Fe Co Ni Cu Zn

OS 3 2,3,4 3,4,6 3,4,5 2-7 2,3,4 2,3,4 2,3, 1, 2,3 2

Some undergo oxidation of the TM cation, eg NiO Oxygen gain : NiO1+d Ni2+/3+
Some undergo reduction of the TM cation, eg. TiO 2 Oxygen loss : TiO2-d 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
La doping of BaTiO3 (n-type doping)
3+

La3+ for Ba2+ ≡ donor

Some electronic
configurations
d-block elements
K [Ar] 4s
1
Transition Metals
Ca [Ar] 4s2
Sc [Ar] 4s23d1 d1 d2 d3 d4 d5 d6 d7 d8 d9 d10
Ti [Ar] 4s23d2
V [Ar] 4s23d3
Cr [Ar] 4s23d4
Mn [Ar] 4s23d5
Fe [Ar] 4s23d6
Co [Ar] 4s23d7
Ni [Ar] 4s23d8
Cu [Ar] 4s23d9
Zn [Ar] 4s23d10

Ti metal is [Ar]4s23d2

Ti4+ in TiO2 is [Ar]4s03d0

(therefore d0)

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

 NiO
NiO (pale green insulator) → NiO1+δ (black semiconductor)
heat in air at > 1100 oC
• NiO has the rock salt structure

Ni O Ni O Ni 2+ 2- 2+ 2- 2+
O Ni O Ni O 2- 2+ 2- 2+ 2-
Ni O Ni O Ni or 2+ 2- 2+ 2- 2+
O Ni O Ni O 2- 2+ 2- 2+ 2-
• NiO1+δ or Ni1-xO
• When heated in air, NiO picks up O2 molecules which adsorb on the surface,
dissociate and pick up 2e to form O2-.
• These electrons come from oxidation of the Ni2+
½O2 + 2e- → O2-
Ni2+ is (d8) whereas Ni3+ is (d7) 2Ni2+ → 2Ni3+ + 2e-
• To partially balance the extra layer of O2- ions at surface, Ni2+ ions migrate
leaving cation vacancies throughout the crystal
• So each extra O2- generated creates one Ni vacancy (somewhere) and two Ni3+
ions
• So general formula Ni1-xO becomes Ni2+1-3xNi3+2xO
 Oxidation of NiO
O2 gas molecules

O-O O-O O-O

(i)
O O (ii) O2- O2-
Ni2+ O2- Ni2+ O2- Ni2+ O2- Ni2+ O2- Ni3+ O2- Ni3+ O2-
1200 C o (iii)
O 2- Ni2+ O2- Ni2+ O 2- Ni2+ O2- Ni2+ O 2- Ni3+ O2- Ni3+
Ni2+ O2- Ni2+ O2- air Ni2+ O2- Ni2+ O2- Ni2+ O2- Ni2+ O2-

O 2- Ni2+ O2- Ni2+ O 2- Ni2+ O2- Ni2+ O 2- Ni2+ O2- Ni2+

Ni2+ O2- Ni2+ O2- Ni2+ gas
(i) Oxygen O2- molecules
Ni2+ Odissociate
2- Ni2+ O2- Ni2+ O2-
• Stoichiometric NiO crystal
from2-the air and 2-form adsorbed (iv) Ni ions migrate from the
O 2- Ni2+ O2- Ni2+ O Ni 2+
monatomic O atoms O Ni2+ the
onto O 2- to
crystal Nithe
2+
O2- Ni
surface
2+
to form a
• Pale-green in colour
surface of the NiO crystal new layer of NiO on the surface
(ii) These oxygen atoms are reduced of the crystal. This creates some
• Electrical insulator
to O2- ions, i.e. O + 2 e- → O2- metal vacancies in the crystal
• All Ni2+ (d8) (iii) Some Ni2+ (d8) ions are oxidised to
Ni3+ (d7) ions (i.e. Ni2+ → Ni3+ + e-)
as they supply the electrons for
the reduction of the surface O
atoms.
 O2- O2- (iv) O2- Ni2+ O2- Ni2+ O2- Ni2+
Ni2+ O2-
Ni3+ O2- Ni3+ O2- Ni2+ O2- Ni3+ O2- Ni2+ O2- Ni3+ O2-
1200 oC O 2- Ni2+ O2-
25 oC
O 2- Ni3+ O2- Ni3+ O 2- Ni2+ O2- Ni3+ O2- Ni3+ O2-
Ni2+ O2- Ni2+ O2- Ni3+ O2- Ni3+ O2- O 2- O2- Ni2+
air air Ni2+ O2- Ni2+ O2-
O 2- Ni2+ O2- Ni2+ O 2- O2- Ni2+ O 2- Ni3+ O2- Ni2+
Ni2+ O2- Ni2+ O2- Ni2+ O2- Ni2+ O2-
• Non-stoichiometric NiO crystal
(iv) Ni ions2+migrate from2+the [NiO1+x (oxygen excess) or
O 2-
Ni O 2-
crystal to the surface toNi form a O 2- Ni3+ O2- Ni2+
Ni1-xO (metal deficient)]
new layer of NiO on the surface
of the crystal. This creates some
• black in colour
metal vacancies in the crystal

Vacant metal sites on surface of • Electrical semiconductor

crystal
• Mixed Ni2+ (d8) and Ni3+ (d7)

• Hopping semiconductor
 Ni1-xO
Cation vacancy
2+ 2- 2+ 2- 2+ 2- Slope = -E/k
2-  2- 2+ 2- 2+
n = [Ni3+]
2+ 2- 2+ 2- 3+ 2- ln σ
2- 2+ 2- 2+ 2- 2+
2+ 2- 3+ 2- 2+ 2-
2- 2+ 2- 2+ 2- 2+
1/T
• Black ‘NiO’ is a p-type hopping semiconductor because electrons hop
from Ni2+ to an adjacent Ni3+ (or the positive holes, ie Ni3+, hop in the
opposite direction)
• Electrons are localised on the Ni2+ so the concept of conduction and
valence bands does not apply. The main conduction process is:
Ni2+ → Ni3+ + e
• This is an activated energy process so that an activation energy is need
to get the electrons to hop, slope = -E/k and number of carriers =[Ni 3+]
• It is difficult to control the degree of oxidation so n varies and
consequently so does σ.

Hopping conductivity model as opposed to a band picture model

 Control of oxidation
• One way to control [Ni3+] is to dope with Li+ and obtain Ni1-xLixO

2Ni2+ → Ni3+ + Li+ and the compound becomes Ni2+1-2xNi3+xLi+xO

• Then [Ni3+] and σ are controlled by x, ie Li+ Li+ + h+ → Ni2+

• Ni1-xLixO is a good example of a solid solution. The material has a rock

salt structure with Ni3+, Ni2+ and Li+ distributed at random over the crystal
octahedral sites.

• When x is fixed, then at a fixed field E, σ is controlled.

• Because σ = f(T), then a material such as this can be used for

temperature control as a thermistor (THERMally sensitive resISTOR)

• measure conductivity and read-off the temperature

ln σ
See NiMn2O4 Thermistor
experiment in 1st year lab.

1/T
 Thermistor Practical.
Equations used from lectures.
1 (b)

1 (a) V=IR

3 ρ = RxA/l
5
2
σ = ρ-1
σ = A exp(-E/kT)
Information provided.
• Dimensions of Thermistor
• V to T conversion table for
4
K-type Thermistor

1. (a) Two terminal (Pt-wire) conductivity rig for the sample ((b) NiMn2O4 Thermistor)
2. Electrometer to record Resistance, R, of the sample (as a function of T)
3. Thermocouple (K-type) in close proximity of the sample.
4. Electrometer to record Voltage, V, from the thermocouple (as a function of T)
5. Furnace, to heat the sample.
 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.
• For d0 cations the d band is empty. Insulators – case (a) TiO2, V2O5 (d0)
• For some d e- containing compounds we have partially filled d-band.
Metals – case (b).
Metal s and p Ti2O3, VO2 (d1)
bands

Metal d band
Ef
Eg

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

Partially filled
Ti, 3d-band Empty CB 3d band
e- e- e-
Eg ED (La)

O, 2p-band Full VB

Pure BaTiO3 • Semiconducting

(d0) insulator (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+ Mg2+ TM2+ eg. 0.9 Ǻ 0.86 Å Ni = 0.83 Å (CN = 6)

Na+ Ca2+ eg. 1.16 Å 1.14 Å (CN = 6)
Si4+ Al3+ eg. 0.40 Å 0.53 Å (CN = 4)
Zr4+ Y3+ Ca2+ eg. 0.86 Å 1.04 Å 1.14 Å (CN = 6)
V5+ Mo6+ eg. 0.68 Å 0.73 Å (CN = 6)
La3+ Ba2+ eg. 1.71 Å 1.50 Å (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
 Anions are large

Cation size decreases

Cation size increases

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