Lecture 4: Point Defects, Nonstoichiometry and Controlled
Atmosphere Processing of Oxides
Interstitial
Vacancy
Point defects control many important materials properties:
• Diffusion
• Electrical Conductivity
• Thermal Conductivity
• Ionic Conductivity
• Yielding
• …… 1
• Defects in Ionic Crystals
Ceramic crystal: MaNbXc
Defects in ceramics are more complex than metals or
semiconductors (i.e., Si, Ge, GaAs)
• Defects can occur on either M, N or X lattice sites
• Combinations of cation (M, N) and anion (X) defects are
possible
• Defects and defect concentrations will be atmosphere
dependent (i.e., PO2 for oxides)
• Defects must maintain charge balance (i.e., charged atomic
and electronic)
• Atomic and electronic defects can be associated (charge
coupled) or diassociated (ionized) depending on the
temperature
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Point Defects in Stoichiometric Compound (ionic)Crystals
Cl – Cs+
Cl –
Na+
Anion (more electronegative)
Cation (more metallic) Mostly nonmetallic elements
e.g.: O, N, C, S, Cl
V = vacancy MX
i = interstitial Excess charge associated with
the site (X = 0, • = positive,
Kröger – Vink notation: ’ = negative)
Entity occupying the defect
site (M, X, or V, or a Type of site being 5
substitutional element) occupied (M, X, or i)
Point Defects in Compound Crystals
Excess charge associated with the site (X = 0, • = positive, ’ = negative)6
Intrinsic defects in ionic crystals
Frenkel defect: vacancy-interstitial pair
Schottky defect
vacancy-vacancy pair
Point Defect Thermodynamics
Three balance rules
Mass balance Charge balance Site balance
Steps in Point Defect Thermodynamics
Step I: Write the defect equilibrium reaction
Step II: Write the equilibrium constant
Step III: Write the electro-neutrality condition (ENC)
Step IV: Solve for defect concentration/fraction
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Example: Schottky defect in MgO
Step I: Write defect equilibrium reaction
Step II: Write equilibrium constant
ln
Step III: Write ENC
‐ H’/k
Step IV: Solve for defect concentration
1/T
H’ is the formation enthalpy/energy per defect
Example: Schottky defect in Nb2O5
Step I: Write defect equilibrium reaction
Step II: Write equilibrium constatnt
ln
Step III: Write ENC
‐ H’/k
1/T
Step IV: Solve for defect concentration
H’ is formation enthalpy/energy per defect
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Intrinsic excitation across bandgap
(electron-hole equilibrium)
c F
ni N c exp
kT
F V
pi NV exp
kT
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Examples of defect equilibrium reactions
1. Defect pair formation by intrinsic excitation
is the bandgap energy
2. Schottky defect in Nb2O5
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3. Frenkel defect in MgO
is enthalpy of formation per defect
4. MgO doped with Al2O3
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5. (a) Y2O3-stabilized zirconia (YSZ)
(b) CaO-stabilized zirconia (CSZ)
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Intrinsic and Extrinsic Defects
Intrinsic defects: Formation not induced by foreign species
Extrinsic defects: Formation induced by foreign species
Example: CdCl2 addition to NaCl
At high T:
At low T:
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Non-stoichiometry
We call an oxide MaOb stoichiometric, if M and O are in
the exact ratio, a/b. When this ratio deviates from a/b,
the oxide is called non-stoichiometric. In oxides, mostly two
types of non-stoichiometry are encountered.
Examples: Stoichiometric Non-stoichiometric
Metal deficient FeO Fe1-xO
Oxygen deficient TiO2 TiO2-x
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Non-stoichiometric Oxides
(defects creation via
environmental changes)
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Defects in Non-Stoichiometric Compounds
FeO (Wustite): O content can vary by changing the external O2 pressure
Fe1-xO
The Fe-rich limit: Fe0.95O
Fe vacancies
Fe2+ to Fe3+ At 1200 C, the oxygen
content in FeO can be
varried with oxygen
FeO on the left side of pressures between 10-9
the phase diagram and
Oxygen in increasing and 10-12 atm.
on the right side of the It is very low oxygen pressure, then how
diagram. from this low oxygen pressure oxygen can be
introduced into the lattice site of the FeO?
Lattice parameter and With increasing
Iron vacancy, Density is also
density changes decreasing with
Lattice parameter
indicate cation vacancy is decreasing. increasing Fe
vacancies?
related non-stoichiometry
Other Types:
TiO2 and ZrO2: Oxygen vacancies
ZnO: Interstitial Zn
VO..
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Kröger-Vink Diagram
The degree of non-stoichiometry is determined by the concentration of these point defects
that can be controlled by PO2 and T. The PO2 and T dependence of the defect
concentration can be predicted by equilibrium thermodynamics leading to the
construction of so called Kröger-Vink diagrams.
Consider a case where an oxide MO contains predominantly oxygen vacancies at low PO2
and oxygen interstitials at high PO2. In the intermediate region, the oxide is stoichiometric
and may have anti-Frenkel disorder. For the sake of simplicity, assume that the defects
are doubly ionized.
Possible Defect Equilibrium Reactions
- At low PO2: Kv
- At high PO2: Ki
- At intermediate PO2:
(a) Intrinsic disorder Ko
(b) Anti-Frenkel Kf 23
Electro-neutrality Condition (ENC)
Solve for Defect Concentration
I. At Low PO2
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II. At High PO2
III. Stoichoimetric Region
(b) Anti-Frenkel Disorder
(a) Intrinsic Disorder
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Interaction of Defects and The Environment
Example: MX exposed to M vapor
electron Kröger – Vink diagram:
Vapor pressure
of metal
Frenkel
Electron – hole
equilibrium
Electroneutrality hole
At low PM:
At medium PM:
At high PM:
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Interaction Among Defects and The Environment
Example: MX exposed to M vapor
Kröger – Vink diagram:
Example:
At low PM: dominate
At low PM:
At medium PM:
1 1 KF At high PM:
ln[ M i ] ln( K F' PM ) ln 28
2 2 Ki
D.M. Smyth 29
Usefulness of Kroger-Vink diagram
a) Kroger-Vink diagram for intrinsic (dotted line) and CaO-doped
(solid line) ZrO2; b) the total conductivity for CaO-doped ZrO2 vs. PO2.
Defects created by external sources such as by introducing
dopants, for example, CaO-doped ZrO2
CaO CaZr VO OO
Created oxygen vacancies make this material a good oxygen
ion conductor used in fuel cells and oxygen sensors
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Kroger-Vink diagram provides ranges of T and PO2
Experimental Determination of Defect Type
2+ 4+ ....
Example: Adding CaO to ZrO2 V O
..
Zri ..
Ca
i
Zr0.85Ca0.15O1.85
XRD: lattice parameter = 5.131Å Unit cell volume = 135.08Å3
..
If VO formed, the calculated density = 5.57 g/cm3
Unit cell weight
..
If Zri and Cai formed, the calculated density = 6.01 g/cm3
....
Zr0.85Ca0.15O2
..
V O
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Experimental Determination of Defect Type
Example: ZnO at low O2 pressure
Question: Is interstitial Zn singly or doubly charged?
Singly:
1/ 2 2
Doubly: K P [ Zni ][n' ]
O2
K 1/ 3 1/ 6
2 [ n' ] 1/ 3
PO2
2
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Conductivity is found to be proportional to
References
Main:
The Defect Chemistry of Metal Oxides by D. M. Smyth, Oxford University press (2000)
Other:
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