In: Other
4 (a) Derive a relation for the oxygen pressure dependence of
electrical conductivity in NiO.
(b) Discuss the effects of Cr2O3 additions on the electrical
conductivity of NiO, giving equations describing the temperature at
which the conductivity changes from intrinsic to extrinsic in
relation to the impurity concentration.
SOLUTION:-
A)
In the various oxygen pressures, we investigated the
temperature dependency of the electrical conductivity (σ) of NiO.
It changes from the form A exp (-E/kT) to A' exp (-E/2kT) with the
increase of oxygen pressure (P:10-3~760 mmHg).
From this change we can determine the unique value of the
activation evergy E. E=1.25 eV. The dependency upon the oxygen
pressure at a definite temperature can be expressed generally,by
the formula, σ ∞ Px1.
If we assume, as usual, that when the oxygen pressure increases,the
nickel ions moves towards the surface to react with oxygen and
extend the lattice of NiO, leaving vacant lattice points on the
nickel lattice of NiO, and that such vacant lattice points form the
impurity levels, then we can obtain the relation σ ∞ P41.
Experimental value of x is 3.7 at 1000°,almost in accord with the
above-mentioed result. But at lower temperatures we gain the
smaller value of x,until finally it reaches to the relation σ ∞ P.
And with such assumption,we cannot explain the change of the
temperature dependence of the conductivity in the different oxygen
pressures.
So,we assume that the nickel ions which left the normal lattice
points,partially extend the lattice NiO at the surface,and
partially occupies the interstitial positions. Then, thenumber of
the vacant lattice points (Nh) is proportional to √P,and the number
of the interstitial nickel ions (Nf) is inversely proportional
to√P.
So the number of electrons at the imprurity levels,and of positive
holes in the full band varies depending upon the oxygen pressure.
Using these relations,we can derive the theory which may account
for the experimental data.
From our data,we get a constant δ=Nf/h ~ 2 × 10-3 at 1000°, P=760
mmHg, in which n denotes the number of free positive holes. This
value of δ is very small, nevertheless the effect of this small
value is very serious
B)
The electrical conductivity of single crystals of
α-Al2O3 doped with Cr2O3 (0.03–2.5 wt%), NiO (0.75 wt%) plus Cr2O3
(0.03–0.15 wt%), and NiO (0.75 wt%) has been measured under 1 MeV
electron irradiation at 300 K to investigate the effects of the
concentration of impurity and of the depth of impurity levels in
forbidden bands on the radiation induced conductivity (RIC).
The RIC of Cr2O3 and/or NiO doped α-Al2O3 decreases with increasing
concentration of Cr2O3 and/or NiO dopants. The electrical
conductivity of 2.5 wt% Cr2O3doped α-Al2O3 is smaller than any
other doped materials tested.
The dose rate exponent for Cr2O3 doped α-Al2O3 is smaller than that
for NiO plus Cr2O3 doped material, due to deeper trapping centers
of Cr (5.8 eV from the conduction band) than those of Ni (2.0 eV).
Doping impurities with deep trapping centers are most effective for
suppressing RIC.