Vous êtes sur la page 1sur 26

What is a defect?

Fundamental definition:
Any deviation from the perfect crystal is a defect!

- Macroscopic defects (porosities, cracks)

- Atomic defects

- Electronic defects

Let us first consider whar a defect really is. As shown in the slide the fondamental
definition is that any deviation from a perfect lattice is a defect. One type is the
macroscopic defects like porosities and cracks, which have an overall negative
influence of mechanical as well as electrical properties of a material. In the
fabrication of electroceramics these macroscopic defects are diminished as much
a possible i n the fabrication of high density and crack free materials.
The defects which directly influence the electrical properties and on which we
shall focus here are of two types: the atomic defects and the electronic defects. In
he following slides we consider these defects in greater detail.

3
Atomic (point) defects in Oxides!

Missing ions:
- oxygen ions,
oxygen vacancies
- cations,
cation vacancies

Substituted ions
Interstitiel ions 4

Important atomic defects or as they also are called, point defects, in oxides are
shown in this slide. These comprises missing oxygen and cations, which give rise
to vacancies, i.e. oxygen vacancies and cation vacances. The second class of
point defects is the substituted cations and the effec of this substitution depend
on the charge difference in charge and size between the host cation and the
substituting cation.It is however seldom that the anoins are substituted in oxides.
Finally there are the ions in nterstitial positions, which are empty in the pure
lattice. Both anoins and cations can jump to interstitial positions.

4
Electronic defects in oxides


 


 


 
 
5

In Lecture Notes I – Electroceramics we have already introduced the electronic


defects, the electrons and the positive holes.There we saw that electrons in the
crystal are placed in energy levels, the so-called energy band model. The two
bands determining the electrical pproperties are the valence band and the
coduction band which are separeted with the so-calles forbidden band gap where
the electrons are not allowed. We als saw that a positive hole is formed when an
electron jump from the valence band across the band gap to the conduction
band. A posive hole is thus a missing electron in the valence band wth a relative
charge of +1.
Contrary to the point defects, where the type and properties depend on their
position in the lattice, the electronic defects, i.e. electrons and positive holes,
depend the energy levels available for the electrons which spread out over the
whole crystal.

5
Defect notations
subscript
(Symbol for type)position

VO = vacancy on oxygen position


VM = vacancy on metal position, VFe

Oi = interstitial oxygen ion


Mi = interstitial cation

YZr = Y-ion on Zr-ion position


6

In order to be able to express the formation of defects in the form of a chemical


reaction we need have symbols to describe the defects. The notation used here
is the so-called Kröger – Vink notation, introduced by the the two american
scientists in 1956.
As shown in the slide a symbol decribes the type, V for vacancy for instance with
a subscript added which gives the position in the lattice, it can be an oxygen
position, a cation position, an interstitial position or the postion of a substituted ion
sitting on the position of a host cation. Some examples are presented in the slide.
Study these!

6
Charges of defects
Relative charge
Charge relative to the charge normally
present in the position of the defect

Examples:
ZrZr – relative charge = zero, FeO:
but Fe2+ vacancy – rel. ch. = ?
YZr - relative charge = -1
-2 of course!
ZrY ? Rel. ch.+1
7

Besides the symbol for the defect and its position it is also important to indicate
the charge, or rather the relative charge of the defect. As indicated in the slide we
talk always of relative charges, i.e. the charge relative to the charge normally
present in the position where he defect is sitting.
Eaxamples are presented in the slide:
Zr4+ sitting on a Zr4+ site has of course a zero relative charge. But if Zr4+is
substituted with Y3+ , which is expressed as YZr, then the relative charge becomes
-1. Or if Y+3 is substituted with Zr4+ then the relative charge becomes +1.
Study also the example of an Fe2+ vacancy.

7
Charges of oxygen vacancies
Formation of oxygen vacancies:
Oxygen atoms are removed from the crystal

Oxygen ions – how many electron in outer orbital ? 8


Oxygen atoms – how many electrons in outer orbital ? 6
Oxygen vacancy – how many electrons left ? 2
Rel. Charge ? Zero!
But these electrons can easily migrate to neighbouring ions
forming vacancies with one or zero electrons present.

Thus VO with rel. charges of zero, +1 and +2 can be formed !


8

Now that we have seen how to write the symbols and the relative charges for
different types of defects, we shall in this slide study 1) how oxygen vacancies
are formed, and 2) what relative charges xygen vacancies can have.
First the formation of oxygen vacancies: As explained on the slide, it is oxygen
atoms which are removed from the crystal, for instance at low oxygen pressures
(reduction). Well it is well known that the oxygen ions have 8 electrons in their
outer orbital, valence electrons, which of course give an real charge of -2 (but a
relative charge of zero as discussed previously). On the other hand an oxgen
atom has only 6 electron in the outer orbital, and removing an oxygen atom will
therefore leave two electrons in the oxygen vacancy. This oxygen vacancy will
therefore have a relative charge of zero.
As also explained in the slide, the two electrons are only loosely bound and they
can therefore relatively migrate to neighbouring ions, preferably cations. The
relative charges of oxygen vacancies can therefore be zero, +1 or +2 dependin
on whether 2,1 or zero electrons are presnent in thje vacancy.

8
Relative charges of interstitial ions

O2- ions,Oi ? -2

Cl-1 – ions, Cli, rel. charge = -1

Na+1 – ions, Nai , ? +1

Zr4+ - ions, Zri, rel. charge = +4

When O2-jumps to an intersitial position with th chage zero, an interstitial oxygen


ion naturally will have a relative charge of -2.
Other examples are shown in the slide. Study these!

9
Formation of defects
Three typical areactions:

- ”high” temperatures, INTRINSIC DEFECTS

- reaction with surrounding atmosphere

- substitution

13

Let us now consider how defects are formed. As shown on this slide typical
reactions are: 1)intrinsic reactions, i.e. reactions characteristic of the material
itself without the influence of foreign substances, at high temperatures where the
lattice becomes partially unstable due to thermal vibrations. These defects are
also termed as ”thermal defects”; 2) reactions with the surrounding atmosphere,
for instance reductions at low oxygen pressure or oxydations at high oxygen
pressure, and 3) substitutions with aliovalent cations, i.e. Cations with a different
valence than that of the host lattice.

13
Intrinsic defects
Pair of defects:

-Frenkel defect:
cation vacancy and interstitial cation
-Anti-Frenkel defect:
oxygen vacancy and interstitial oxygen ion
-Schottky defect:
oxygen vacancy and cation vacancy
MO: OOx + MMx = VO•• + VM
M2O3: 3OOx + 2MMx = 3VO•• + 2VM
Stoichiomtry must be maintained ! 14

Let us first look at the intrinsic defects formed at high temperatures. As shown, these defects are
generally formed in pairs, which means that the stoichiometric composition is always maintained.
Generally we have three types of defects traditionnaly named after the scientists which originally
introduced these defects:
1)Frenkel defects, which are formed when a cation is jumping into an interstitial position leaving
behind a cation vacancy. This can be expressed by the reaction in a MO oxide:
MMx = VM + Mi•• ;
2) Anti-Frenkel defects, which are formed when an oxygen ion is jumping into an interstitial
position leaving beins an oxygen vacancy as expressed by the reaction (MO oxide)
OOx = VO•• + Oi ;
3) Schottkey defects, which are formed when both an oygen ion and a cation leaves the lattice, for
imstance by evaporation from the surface of the crystal. In this case oxygen vacancy – cations
vancancy pairs are formed. The reactions in respectively a MO an a M2O3 oxide are shown on
the slide. Please note that stoichiometry is maintained in both reactions.

In all reactions it is also clear that electrical neutrality is stricly obeyed. It is of course not possble
create an electrically charged material by these reactions.
Finally it may seen odd to use these designation for defect-pairs but this is nevertheless how they
often are designated in the litterature.

14
Defects formed in an reaction
Reduction
with surronding atmosphere.
MO2 = MO2-x+ x/2 O2

OOx + 2MMx = VO•• + 2MM + 1/2O2

Oxides with cations


easily reduced!

15

In this slide we shall look at how oxygen vacancies are formed in a reaction
(reduction) with the surrounding atmosphere at low oxygen pressure. First we can
note that this reduction leads to the formation of a nonstoichiometric compound,
an oxygen deficient compound as expressed in the overall reaction shown on top
to the right.
As shown earlier (slide 8 ) it is the oxygen atoms which are removed from the
lattice, not oxygen ions. This leaves a vanacy behind with two electrons, which
creates a neutral oxygen vacancy VOx and which easily are ionized into a single
charged vacancy with one electron, VO•, and an empty double charged vacancy,
VO••. The electrons liberated from the vacancies are captured by the cations
which therefore are reduced from MMx to MM.
The reaction of formation of double charged oxygen vacancies and reduced
cations, called compensating defects, are shown on the slide.
Finally it should be noted that this reaction only can take place in oxides where
the cations are easily reduced. The dominating defect in these oxides are
therefore oxygen vacancies.

15
Defects formed in a reaction with
Oxidation
a surrounding atmosphere - 2
MO + y/2O2 = M1-yO

Note – clusters !

Cations easily oxidized!

16

But how will the reaction be in an oxidation in an oxide with easily oxidized cations, in this case a
MO oxide.
Well, in this case oxygen atoms from the atmospere are first adsorbed to the surface of the
crystal. For the formation of oxygen ions we need two extra electrons for each oxygen atom (see
slide 8) which are provided from neighbouring cations which then are oxidized – in these cations a
valence electron is removed forming a positive hole in the valence band for these cations. In such
reactions it is however also necessary to maintain the ratio between the two types of sites, i.e. the
oxygen ion and the cation sites. Empty cation sites, in fact cation vacancies, are therefore formed
in the surface in positions adjacent to the adsorbed oxygen ions. By diffusion these surface-
vacancies are however quickly filled up with cations from the interior, and the cation vacancies
are movng inwards forming defect clusters of different types as well as free cation vacancies. The
formation of VM is shown on the slide
As shown we can have the following types of defects:
VMx = [VM 2MM•] x, where one cation vacancy is attached to two oxidized cations;
VM = [VM MM•],where one cation vacancy is attached to one oidized cation;
VM which is an empty cation vacancy.
It is important to note the difference to oxygen vacancies, which can contain two, one or no
electrons. In the case of cation vacancies it is nonsense to speak about vacancies containing one
or two postive holes, as these always will de present in the valence band of the cations.
Finally it is interesting to note that the dominating defects in oxides which are easlily oxidized are
cation vacancies. The general formula for such oxides is therefore M(1-y)O

16
Formation of interstitial
oxygen ions- Oi
High oxygen pressures !

1/2 O2 + 2MMx = Oi + 2MM•

Oxides where cations are easily oxidized – FeO

17

Oxygen ions can also be formed in interstitial positions at high oxygen pressure .
The reaction is shown on this slide. In this case the electrons needed to form
oxygen ions are provided from adjacent cations which becomes oxidized as for
the formation of cation vacances discussed on the previous slide. He formation of
interstitial oxygen ions thus preferentially takes place in osides which are easily
oxidized.

17
Defects formed by substitution!
Substitution of cations !

Lower valency: Higher valency:

ZrO2 doped with CaO: Y2O3 doped with ZrO2:

CaO(ZrO2) = CaZr + VO•• + OOx 2ZrO2(Y2O3) =


Oxygen vacancies formed to 2ZrY• + Oi + 3OO
maintain electrical neutrality !

Same valency?
18

Let us finally consider how defects can be formed by substitution of the cations.
As shown on this slide the defects formed depend on the valency of the
substituting cations relative to the valence of the host cations. If the valencies are
different the substituting cations are called aliovalent cations.
If the valence is higher, for instance when ZrO2 is doped with CaO as shown to
the left , Ca2+ will replace Zr4+ions forming the defect CaZr. In order to maintain
electrical neutrality it is necessary that a positively charged defect is formed,
which in this case is an oxygen vacancy, VO••. Doping zirconia with an oxide with
a cation with a lower valence is thus an efficient way to form good oxygen ion
conductors as will be discussed later. Another dopant very much used in zirconia
is yttria, Y2O3.
To the righ is shown what happens when the dopant has a higher valency, as for
instance when yttria is doped with zirconia as discussed here. Well, the defect
formed by the substitution will in this case be ZrY• and the compensating defect
with an opporsite charge will in this case be interstitial oxygen ions, Oi.
But what happens when the dopant has the same valency as that of the host
lattice, for example in MgO doped with CaO?
No defects are of course formed, but it can have an effect if the two are ions have
different sizes. This will create tensions in the lattice which can have an influence
on for instance the mechanical properties of the material.

18
Dependence on oxygen
pressure

Can defects in a solid be considered as ions in a solution?

Yes if these conditions are fulfilled:


- random distribution of defects
- no interactions
- high mobility

Law of mass action can be used. 21

In this section we shall use our knowledge about defect notations and defect
charges first to express the formation of different types of defects, and then using
the mass action law to find the dependece of defects concentrations on the
oxygen pressure. One example is shown on this slide for the formation of oxygen
vacancies and reduced cations in nonstoichiometric cerium oxide (Eq.1).
A fondamental question is of course, whether one can use the mass action law in
a solid. Well if the three conditions indicated on the slide are fulfilled it is possible
to use the mass action law, just as it is possible to use it on chemical reactions
taking place in a liquid.

21
Rules which must be obeyed

• ratio between cation and anion positions – Constant!

• the total number of positions can be changed,


but not the ratio!

• neutrality must be maintained

22

In setting up reaction schemes for defect formation in a solid, the three rules
given on the slide must however be obeyed. The two first rules naturally comes
from the fact that the reactions are taking place in a solid with a fixed ratio of
anion – and cation sites, which must be kept constant. If this rationis changed
then another phase with another composition and structure is formed and this
changes the conditions completely.
The last rule of maintaining neutrality is evident, it is not possible to create ”a
charged material” with these processes.

22
Formation of oxygen
vacancies

23

But let us now look at the formation of oxygen vacancies and reduced cations in
CeO2-x.
First we have the reaction as explained previously. If we use the mass action law
on this reaction, the K(T) expression is obtained – here K(T) means the
equilibrium constant at constant temperature T, all the a(...) values the activities
of the different species and p(O2) of course the partiel pressure of oxygen.
Now as indicated on the slide, the solid phase where the reaction is taking place
can thermodynamically be consirered as a ”non-ideal solution”, which means that
the activity of the defects is proportional to the concentration of the defect, c or
[..], times he activity coefficient,  (gamma), which can be considered constant
within a relatively small compostion range.
Replacing the activity terms in the K(T) expression we obtain the K(T) expression
where all the  values are included in the constant. As this reaction describes the
formation of oxygen vancies, VO••, so the equilibrium constant is naturally
designated as K(VO••).

23
[VO] ∝ log pO2
1

24

In order to carry on we need to consider the neutrality condition. From the


equation for the edefect formation (Eq.1) we can see, that eact time one oxygen
vancancy is formed two reduced cations are formed to maintain the charge
balance. As shown on the slide, the neutrality condition must be that the
concentration of the reduced cations must be twice the concentration of the
oxygen vacancies, as also shown in this simple neutrality condition.
Now replacing the concentration terms for the reduced cations with
conccentration terms for the oxygen vacancies we get equation 2 from which it is
easy to see that the concentration of oxygen vacancies is proportional to the
oxygen pressure raised to the power of -1/6. This exponent is in fact
characteristic for the formation of oxygen vancancies in any oxide.

24
Brouwer plots - VO

25

A good way to present the characteristic defect concentration – oxygen pressure


relationship is to use a so-called Brouver plot named after an american scientist.
In this plot the logarithme of defect concentration is plottet against the logarithme
of the oxygen pressure which in the case ofoxygen vacancies will give a straight
line with a slope depending on the type of oxygen vacancy. In the case of VO••
this slope will of course be -1/6. The characteristic slopes for neutral and single
charged vacancies are also shown on this plot.
Next slide – practice!

25
[VM] ∝ log pO2

28
5

In this slide we shall look at the formation of VFe which as shown in slide 16
typically is formed by oxidation of an oxide which is easily oxidized as FeO.
As shown in equation 1 this double negatively charged iron vacancy iis formed
together with two oxdized cations and an oxygen ion in an oxugen position in the
lattice – as explained earlier, the oxygen atoms in the atmosphere need two
electrons forthe formation of oxygen ions and these electron are delivered by
adjacent Fe2+ ions, which become oxidized.
The resulting equilibrium constant K(Ve) is shown in eq. 2, and the neutrality
condition in eq. 3 – that the neutrality condition must be ike shown in eq. 3 is of
course quite clear, as two oxidized cations are formed for each VFe, and the
concentration of oxized cations must therefore be twice that of VFe.
Inserting this neutrality condition into eq.2 gives the expression for K(VFe) (eq.4),
which naturally leads to eq. 5 which shows that the concentration of VFe is
proprtional to the oxygen pressure with an exponent of +1/6. The exponent for
the formation of cation vacancies thus has the same value but with opposite sign
as compared to the exponent for the formation of oxygen acancies.
Finally note that the concentration of the iron vancancies correspond to the
deviation, y, from the stoichiometric composition.

28
Brouwer plots - VM

29

The Brouwer plots for the three types of iron vacancies will thus also be straight
lines but with slopes of 1/6, 1/4 and ½. From this slide you should also note single
charged and neutral vacancies in fact consists of clusters with the compositions
shown.

29
Brouwer plot for Oi

32

Let us finish by looking at the dependence of the concentration of interstitiel


oxygen ions on the oxygen pressere.
The formation of interstitial oxygen ions by oxidation is shown in eq. 1, the
neutrality condition in eq.2 and the dependence of the concentration of the
interstitial oxygen ions in eq. 3.
Note that the oxygen pressure dependence is the same as that obtained for the
concentration of VFe.
Note also that the formation of the intrinsic anti-Frekel defects (slide 14)
consisting of an oxygen vacancy – oxygen interstitial of course is independent of
the oxygen pressure.

32
Brouwer plot:
many defects
Construction:
- Log Conc. defect
vs log(pO2)
- 3 p(O2) regions;
- one type of defect
dominates in each
region
- sharp transition
between regions,
approximation

33

Let us finally look at a Brouwer plot for a material in which many defect are
possible and which is generally the case. This plot shown on the slide is clearly
much more complicated than the simple Brouwer plots for a sigle defect.
As in the simple Brouwer plots the logaritme to the defect concentrations are
plotted as a function of log (p(O2). Generally three oxygen pressure ranges are
considered, a low pressure region, a medium pressure- and a high pressure
region. For each region straight lines with characteristic slopes are obtained for
each type of defect as in the simple plots.Note also that in this simple
representaion the transition between the pressure regions for a specific defect is
considered to be abrupt. This is of course an approximation, but it is rather close
to reality. Finally it will also be observed that one type of defect is dominant in the
three regions – here it is: low pressure – n, high pressure – p, medium pressure n
and p.
This diagram therefore show the defects in an electronic conductor
For a detailed discussion how the relations ships are calculated for the different
regions and how the diagram is constructed: Introduction to Defects in
Nonstroichiometric Binary Oxides, O.Toft Sørensen should be consulted – can be
obtained from the author (otsdk@yahoo.dk).

33
Calculation of defect
concentrations

• Deviation from the stoichiometric composition.

• Fraction of defects

• Number of defects per cm3

34

In dealing with defect it is of course important t be able to calculate the defect


concentrations. In this slide the three most important mmeasures of defects
concentrations are mentioned

34
Deviation from stoichiometric
composition

35

First the deviation frm the soichiometric composition. In the case of a oxygen
deficient oxide and in oxides this is indicated in the formula with an x, which can
be negative (oxygen vacancies) or positive (oxygen in interstitial positions).
In the case of an oxide with cation vacancies, the presence of these are indicated
with a y written for the cations in order to emphasize that there are vacant cation
sites present.

35
Site Fractions

MO2-x

Fe1-yO

MO2+x

36

The second method to indicate the defect concentration is also very simple – the
site fraction. Examples of fractions of oxygen vacancies and cation vacancies are
demonstrated on the slide. How the fractions depend on the deviation from
stoichiometric compostion is also shown on the slide for MO2-x, MO2+x and M1-yO.

36
Number of defects per cm3

37

Finally the formulas for calculating the defect concentrations as number of defect
per cm3 are shown in this slide for the thRee different types of oxides. These
formulas are quite easy to derive and we shal not do this here. However the
derivations are described in ”Introduction to defects in Nonstoichiometric Oxides
by the author.

37