Defects: Recap

Notation
• Msc - M - main species or vacancy,
Usually called
• s - site, c - charge
Kroger-Vink
• (• and ’ for + and -, x- none) notation)
Examples:
• Co on a Co site: CoCox
′′
• Vacancy on a Co site: 𝑉𝐶𝑜
• (note that the charge is an effective charge and
that when a cobalt ion (usually 2+) is missing, it
leaves behind a “space” with an effective
charge of 2-)
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More examples of notation
• Vacancy on Cl site in NaCl:
• Na in an interstitial site
• Adding a little KCl to KBr - Cl substitutes for Br on
the lattice
• Adding CaCl2 to NaCl:
• Ca substitutes for Na
• Ca goes into an interstitial space
• Possible defects in Al2O3

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Why do defects exist?
• Consider: take an atom off its site and put it on the
surface
• H must be endothermic (breaking more bonds
than forming) - so energy is REQUIRED
• But… it isn’t just H that dictates G: S also
comes in to play.
• Gperf>Gdef so a defective crystal has LOWER energy
than a perfect one!

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Free Energy vs # of defects
Energy to create defect

Free energy gained due to

configurational entropy
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How are Point Defects Introduced?
• Added solutes (extrinsic defects)
• impurities or dopants
• Stoichiometry changes
• cation/anion ratio changes
• Example FeO: Fe is +2, but Fe can also be Fe+3 or Fe+4…If
you could somehow change x mol Fe+2 into x Fe+3, then
you would have 1-x mol of FeO and x mol of Fe2O3
• So now you need MORE oxygens to achieve this
stoichiometry - get them from the air.
• What defect is created in this process?

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Rules for Defect Reactions
• Mass balance
• Can’t create or destroy mass
• Electroneutrality
• Charge can’t be created or destroyed
• Preservation of site ratio
• Parent lattice site ratio must remain intact
• If a cation site is added, an anion site must also be
added (if the ratio is 1:1)

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Site ratio further examined
• Formalizing for MaXb: M M + VM a
• a(XX +VX) = b(MM + VM) =
X X + VX b
• Note that the number of atoms don’t have to have
that ratio

• (Interstitials aren’t considered “sites”)

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Stoichiometric reactions
• Chemistry of crystal doesn’t change
• Schottky (anions and cations)
• Frenkel (usually cation V and cation i)
• Misplaced atoms (also called antisite)

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Schottky defects
• For MO:
• Null (perfect crystal)  VM’’ + VO•• ----------Gs
• Where Gs is the free energy of formation of the
Schottky defect
(Note that negative
• For Al2O3: defect is always
• Null  2VAl’’’ +3 VO•• written first)

Do these reactions follow the “rules”?

mass balance, electroneutrality, site preservation?

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Frenkel Defects
• Vacancy created - cation (or anion) moves from
regular site to an interstitial
• MMx ⇒ VM’’’ + Mi••• GF
or
• Oox ⇒ Oi’’ + VO••

• (Note that negative defect written first)

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Antistructure defects
• Doesn’t occur in ionic ceramics
• Why?

• Example:
• CC + SiSi ---> SiC + Csi

• Is this reaction STILL stoichiometric?

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Nonstoichiometric Defects
• Composition changes as a result of the defect
reaction.
• Mass is transferred across the boundary of the
crystal
• (usually loses or picks up oxygen)
• Low oxygen partial pressure Oox ⇒ ½O2 + Vox
• Oxygen leaves as a neutral species so it leaves its
electrons behind (so the normally + vacancy is
neutral)

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The electron story…
• These electrons are weakly “bound” to the vacancy
- and are usually excited into the conduction band:

• Vox ⇒ Vo• + e’ first ionization

• Vo• ⇒ Vo•• + e’ second ionization

• Combining:

• Oox ⇒ ½O2 + Vo••+ 2e’

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 Other non-stoichiometric defects
• Oxygen can be incorporated as interstitials
• ½O2(g) ⇒ Oix (holes must be attached to interstitial
to neutralize it)
• Holes can be “released”
• Oix ⇒ Oi’ +h•
• Oi’ ⇒ Oi’’ +h•
½O2 (g) ⇒ Oi’’ +2h•

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Transition metals
• In considering what happens to electrons and holes
- we assumed that they became part of the
electronic structure (e.g. either in the conduction
band or valence band)
• …. There is another possibility -
• What is the implicit assumption?

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Example: Magnetite
• Fe3O4 - Spinel structure
• ⅔ are Fe3+ and ⅓ are Fe2+
• ½O2 (g) ⇒ OOx + VFe’’+2h•
• 2Fe2++ 2h• ⇒ 2Fe3+
• ½O2 (g)+ 2Fe2+ ⇒ 2Fe3++ OOx +VFe’’ So, the holes were
used to change the valence of Fe from Fe2+ ⇒ Fe3+

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Extrinsic Defects
• Most crystals aren’t pure
• Often properties are dominated by
impurities(dopants, if intentional)
• How are defect reactions written?
• There are many, many possibilities
• Often very complex
• General rules and standard procedure - help a little

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Extrinsic Defect reactions
• Substitution for host ion closest in electronegativity
is most probable
• Even if the size difference is large
• Cations for cations, anions for anions
• Size CAN matter in covalent compounds
• Why?
• Interstitals are very hard to predict

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General procedure
• Example CaCl2 in NaCl
1. Draw a picture of the host
2. Draw a schematic of the impurity directly over the host
matching ions
3. Look for what is “left over”

Impurity Cl Ca Cl

Cl Na Cl Na
Host Crystal
Na Cl Na Cl

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General procedure
• Example CaCl2 in NaCl
1. Draw a picture of the host
2. Draw a schematic of the impurity directly over the host
matching ions
3. Look for what is “left over”

Impurity Cl Ca Cl V

Cl Na Cl Na
Host Crystal
Na Cl Na Cl

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Possible Defect Reactions
Impurity Cl Ca Cl V

Cl Na Cl Na
Host Crystal
Na Cl Na Cl

• Ca on Na site (CaNa•)
• V on a Na site (VNa’)
• Cl on Cl site (twice)
• CaCl2 ⇒ CaNa•+ VNa’ + 2ClClx
2NaCl

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 Possible Defect Reactions
Impurity Cl Ca

Na Cl
Cl Na
Cl
Host Crystal Na Na Cl
Cl

• Ca on Na site (CaNa•)
• Cl on interstitial Cli’)

CaCl2 ⇒ CaNa•+ Cli’ + ClClx

NaCl
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 Defect equilibria
• Relating concentration of defects to temperature
and oxygen pressure (or other thermodynamic
parameters)
• Generalized reaction: c d
aC aD
• aA + bB ⇔ cC +dD
K= a b
• Equilibrium constant, K
aA aB
• Where ai is the activity raised to the stoichiometric
coefficient

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Defect equilibria
• Defects are structural elements that posses
chemical potential, so equilibria can be expressed
where (a is replaced by mole fractions)
Note that ideality
is assumed - i.e.
activities have
been replaced by
mole fractions

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Ex.: MO at various P(O2)
• Low P(O2):
• Oox ⇒ ½O2(g) + Vo••+2e’ Gred

[V ][ n ]
1
·· 2
PO22
= K red
O

[O ]x
O

• Kred = exp(- Gred /kT)

• Conc. of O on O sites is 1
• [n] = concentration of electrons

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Ex.: MO at various P(O2)
• Moderate P(O2):
• Oox + MMx ⇒ Vo••+VM’’ Gs
[ O ][ M ]
V ··
V ''

= Ks
• Ks = exp(- Gs /kT) [ O ][ M ]
x
O
x
M

• [Oox] and [MMx] are ≈ 1

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Ex.: MO at various P(O2)
• High P(O2):
• ½O2(g) ⇒ Oox + VM’’+2h• Gox

[V
''
M ][ ] [ O ]
p O
2x

= K ox
1
PO22

• Kox = exp(- Gox /kT)

• [p] = concentration of holes.
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Electronic equilibrium
• Null ⇒ e’ + h•

æ -E g ö
[ n][ p] = K i = expç ÷
è kT ø
• Eg is the energy of the band gap

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 At equilibrium
[V ][ n ] P [V ] [ V ] = K
1
·· 2
[VM'' ][ p] [O xO ]
2 ·· '' 2
O2
= K red
O O M
= K ox
[O ] x
O [ O ][ M ]
x
O
x
M
s
1
PO22
æ -E g ö
[ n][ p] = K i = expç ÷ p + 2VO·· = 2VM'' + n
è kT ø
Concentrations all must simultaneously
satisfy these equations (5 eqn. - 4
unknowns)
Also -electroneutrality condition -
 + charges) = - charges)

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 At equilibrium
[V ][ n ] P [V ] [ V ] = K
1
·· 2
[VM'' ][ p] [O xO ]
2 ·· '' 2
O2
= K red
O O M
= K ox
[O ] x
O [ O ][ M ]
x
O
x
M
s
1
PO22
æ -E g ö
[ n][ p] = K i = expç ÷ p + 2VO·· = 2VM'' + n
è kT ø

Concentrations all must simultaneously

satisfy these equations (5 eqn. - 4
unknowns)
Also -electroneutrality condition -
 + charges) = - charges)

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