陶瓷材料 (1021)

Homework 5 – Solution

1. Estimate the number of vacant sites in an ionic ceramic conductor at room

temperature in which the cations are the predominant charge carriers. Assume
that at room temperature the electrical conductivity is 10-17 (m)-1 and the ionic
mobility of 10-17 m2V-1s-1. State your assumptions.

Solution:
Assume zi = 2, and since  i  ci zi ei (c.f. Eq. (3.36))
i 10 17
ci    3.1  1018 m 3
zi ei 2  1.6  10  10
19 17

2. A stoichiometric oxide, M2O3, has a band gap of 5 eV. The enthalpy of Frenkel
defect formation is 2 eV, while that for Schottky defect formation is 7 eV.
Further experiments have shown that the only mobile species are cation
interstitials, with a diffusion coefficient DM, int at 1000K equals to 1.42 x 10-10
cm2/s. The mobility of the holes and electrons were found to be 2000 and 8000
cm2/Vs, respectively. At 1000K, would you expect this oxide to be an ionic,
electronic or mixed conductor? Show your calculation. Assume number of
interstitial sites is equal to twice the number of atomic sites. Additionally, the
molecular weight of the oxide is 40 g/mole, density () is 4 g/cm3. We also
assume that the density of states for holes and electrons is of the order of 1022
cm-3.

Solution:
To solve this problem, the conductivities of the electrons, holes and ions have to
be calculated.
i) For the electrons:

 Eg   5 
( Eq. (2.45)) ne  N C exp    10 22  exp  5   2.5  10 cm
9 3

 2kT   2  8.62  10  1000 

 e  ci zi ee  2.5  109  1.6  10 19  8000  3.2  10 6 (  cm) 1  3.2  10 4 (  m) 1

ii) For the holes:

The number of holes is the same as the number of electrons, but the holes
generally present a slower mobility than the electrons, i.e., h ~ e/4. Hence
 h   e / 4  8  10 5 (  m) 1

iii) For the ionic conduction:

The enthalpy of Frenkel defect formation (2 eV) is substantially smaller than that
of the Schottky defect formation (7 eV). Therefore, number of Schottky defects
would be negligibly small and can be reasonably ignored. Note that the only
mobile species are the cation interstitials. Hence, in one mole of M2O3 there are
2  6.02  10 23  4
 1.2  10 23 atoms / cm3  1.2  10 29 atoms / m 3
40
As stated in the problem, number of interstitial sites is double that number. Thus
 h   2  3
ci  2  1.2  10 29 exp    2.4  10 exp 
29
5   2.2  10 m
24

 2kT   2  8.62  10  1000 

Substituting this into Eq. 3.37
ci zi2 e 2 Di 2.2  1024  (3) 2  (1.6  1019 ) 2  1.42  1010  104
 ion    5.2  107 (  m) 1
kT 1.38  1023  1000
Therefore, the oxide is an electronic conductor at this temperature since
 e   ion

(You need to be very careful about the unit in your calculation for the above
problems.)

(Any queries about the solution or if you have any difficulties in

understanding my lecture, feel free to come in and talk with me
during the office hours.)