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    Module 4: Defect Chemistry and Defect Equilibria: Suggested Reading

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    Tejinder Singh
    This document discusses point defects in ceramic materials. It begins by defining different types of defects such as point defects, line defects, and surface defects. It then focuses on point defects, which include vacancies, interstitial ions, and electronic defects related to deviations from stoichiometry. Different types of point defects are described, including Frenkel and Schottky disorders. Defect equilibria are examined for stoichiometric and non-stoichiometric oxides, with examples given of oxygen-deficient and metal-deficient oxides. The roles of ionic and electronic compensation mechanisms are described. Finally, dissolution of foreign cations is discussed.

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    Module 4: Defect Chemistry and Defect Equilibria: Suggested Reading

    Uploaded by

    Tejinder Singh
    38 views11 pages
    This document discusses point defects in ceramic materials. It begins by defining different types of defects such as point defects, line defects, and surface defects. It then focuses on point defects, which include vacancies, interstitial ions, and electronic defects related to deviations from stoichiometry. Different types of point defects are described, including Frenkel and Schottky disorders. Defect equilibria are examined for stoichiometric and non-stoichiometric oxides, with examples given of oxygen-deficient and metal-deficient oxides. The roles of ionic and electronic compensation mechanisms are described. Finally, dissolution of foreign cations is discussed.

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    This document discusses point defects in ceramic materials. It begins by defining different types of defects such as point defects, line defects, and surface defects. It then focuses on point defects, which include vacancies, interstitial ions, and electronic defects related to deviations from stoichiometry. Different types of point defects are described, including Frenkel and Schottky disorders. Defect equilibria are examined for stoichiometric and non-stoichiometric oxides, with examples given of oxygen-deficient and metal-deficient oxides. The roles of ionic and electronic compensation mechanisms are described. Finally, dissolution of foreign cations is discussed.

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    © All Rights Reserved
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    38 views11 pages

    Module 4: Defect Chemistry and Defect Equilibria: Suggested Reading

    Uploaded by

    Tejinder Singh
    This document discusses point defects in ceramic materials. It begins by defining different types of defects such as point defects, line defects, and surface defects. It then focuses on point defects, which include vacancies, interstitial ions, and electronic defects related to deviations from stoichiometry. Different types of point defects are described, including Frenkel and Schottky disorders. Defect equilibria are examined for stoichiometric and non-stoichiometric oxides, with examples given of oxygen-deficient and metal-deficient oxides. The roles of ionic and electronic compensation mechanisms are described. Finally, dissolution of foreign cations is discussed.

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    of 11

    Module 4: Defect Chemistry and Defect Equilibria

    Materials in general consist of defects which can be divided into a variety of categories such as point
    defects or 0-D defects, line defects or 1-D defects and 2-D or surface defects. These defects play an
    important role in determining the properties of ceramic materials and in this context role of point
    defects is extremely important. In this module, we will learn about various point defects, role of
    stoichiometry i.e. cation and anion excess and deficit, role of foreign atoms on the defect chemistry.
    Subsequently, we will adopt a simple thermodynamic basis for calculating their concentration in
    equilibrium and then will extend the Gibbs-Duhem relation for chemical systems to the defects in
    ceramics considering them to be equivalent to the dilute solutions, an approximation which is fairly
    valid. This will lead us to the determination of defect concentrations as a function of partial pressure
    of oxygen which is an important exercise to establish the defect concentration vs pO2 diagrams,
    called as Brower’s diagrams.

    Suggested reading:

    1. Nonstoichiometry, Diffusion and Electrical Conductivity in Binary Metal Oxides (Science &
    Technology of Materials), P.K. Kofstad, John Wiley and Sons Inc.
    2. Physical Ceramics: Principles for Ceramic Science and Engineering, Y.-M. Chiang, D. P. Birnie,
    and W. D. Kingery, Wiley-VCH
    3. Introduction to the Thermodynamics of Materials, David R. Gaskell, Taylor and Francis
    Lecture 4.1

    Point Defects
     Point defects are caused due to deviations from the perfect atomic
    arrangement or stoichiometry. These could be missing lattice ions from
    their positions, interstitial ions or substitutional ions (or impurities) and
    valence electrons and/or holes.
     Usually, point defects in metals are electrically neutral where as in ionic
    oxides, these are electrically changed.
     Ionic defects
    o Occupy lattice positions
    o Can be either of vacancies, interstitial ions, impurities and substitutional
    ions
     Electronic defects
    o Deviations from a ground state electron orbital configuration give rise to
    such defects when valence electrons are excited into higher energy
    orbitals/ levels and lead to formation of electron or holes.
     Defects are present in most oxides and are easily understood. Hence most
    examples in the following section use examples of oxides.
    Kröger–Vink notation in a metal oxide, MO
    Regular Sites

    Normal or regular occupied metal or cation site MM

    Normal or regular occupied oxygen or anion site OO

    Point Defects

    Oxygen (anion) vacancy : VO

    Metal (cation) vacancy : VM

    Oxygen (anion) interstitial : OO

    Metal (cation) Interstitial : Mi

    Vacant interstitial site : Vi

    Foreign cation : Mf

    Foreign cation on regular metal site : Mfm

    Foreign cation on interstitial site : Mfi

    A normal cation or anion in an

    oxide with zero effective change : x


    MM or OxO

    Charged oxygen vacancy : VO⦁ or VO⦁⦁ (⦁ represents one


    positive charge)

    Charged metal vacancy : VM ′or VM " ( ‘ represents one


    negative charge)

    Charged metal or oxygen interstitial : Mi⦁⦁ 𝑜𝑟 O′′


    i

    Neutral cation & anion vacancies : x


    VM or VOx

    Electron and holes : e′ and ḣ

    Defect Reactions
     Rules for writing defect reactions
    o Ratio of regular cation & anion sites is always constant.
    o Mass balance to be preserved.
    o Electrical neutrality is to be always preserved.
     Both ionic and electronic defect compensations are possible determined by
    the energetics.
     We will assume complete ionization of defects.
    Defect Structures in Stoichiometric Oxides
     Charged point defect is a defect which ready to be ionized and provides a
    complimentary electronic charged defect. Various such combinations are
    possible such as
    o Cation and anion vacancies (VM and VO )
    o Vacancies and interstitial ion of same kind i.e. VO and Oi OR VM and Mi
    o Misplaced atoms (MO & OM ) − interchanged
    o Vacancies and misplaced atoms for same kind of atom (VM + MO )
    o Interstitial and misplaced atoms 𝑖. 𝑒. Oi & MO
    o Interstitial atoms i.e. Mi & Oi

    Among all of these, first two are the most important as these are regularly
    seen in many important oxides. First is called as Schottky disorder while second
    is called as Frenkel disorder.

    a) Schottky Disorder:
     This defect normally forms at the outer or inner surfaces or dislocations. It
    eventually diffuses into the crystal unit equilibrium is reached.

    OO

    VM
    MM

    VO

    Figure 1 Schottky Disorder

    The defect reaction written as

    0 (or Null) ⇌ VM′′ + Vo⦁⦁

     This defects is preferred when cations and anions are of comparable sizes.
     Examples are rocksalt structured compounds such as NaCl, MgO,
    Corundum, Rutite etc..
    b) Frenkel Disorder:

    OO

    VM
    MM

    Mi

    Figure 2 Frenkel Defect

     This defect can form inside the crystal.


     It forms where cations are appreciably smaller then anions

     Defect reaction is written as


    0 ⇌ VM ′′
    + Mï
     In cases, where anions form the disorder, then it is called as Anti-Frenkel.
    Corresponding defect reaction in that case would be
    0 ⇌ VÖ + O′′i

     Examples of compounds showing this defect are AgBr type compounds such
    as AgBr, AgI etc.

    c) Intrinsic Ionization
     Thermal creation of electron hole pair and is depicted by

    0 = é + ḣ
    Defect Structures in Non-stoichiometric Oxides:
     Mainly of two types:
    i) Oxygen deficient (or excess metal)
    ii) Metal deficient (or excess oxygen)

     Nonstoichiometry necessitates presence of point defects and extent of non-


    stoichiometry determines the concentration of Defects.

     In such oxides, electrical neutrality is preserved via formation of point


    defects and electronic changes.
     Intrinsic ionization is always a possibility.
    d) Oxygen Deficient Oxides
     Formation of oxygen vacancies or metal interstitials or both are possible
     Formation occurs only at the surface

    i) If oxygen vacancies are the dominating defects


     Depicted by MO2-x (x is the extent of non-stoichiometry) and overall
    reaction as
    x
    MO ⇌ MO2−x + O2 ↑
    2

     Due to loss of oxygen, possible defect reactions would be


    o Electronic compensation leading to creation oxygen vacancies and of
    electrons
    1
    OO ⇌ VO⦁⦁ + 𝑂2 + 2𝑒́ or
    2

    o Ionic compensation leads to formation of oxygen vacancies and


    reduction of metal ions on their sites
    1
    OO ⇌ VO⦁⦁ + ′
    O2 + 2MM
    2

    ii) If metal interstitials are the dominating defects then,


     Depicted as 𝐌𝟏+𝐲 𝐎𝟐 (y is the extent of non-stoichiometry)
     Possible defect reactions are
    o Ionic compensation leading to the formation of metal interstitials and
    reduction of metal ions on their sites

    MM ⇌ Mi⦁⦁⦁⦁ + 4MM
    ′
    or

    o Electronic compensation leading to the formation of metal interstitials


    and free electrons
    ̀
    M ⇌ Mi⦁⦁⦁⦁ + 4e

     Creation of quasi-free electrons (extra charge is represented as M’)


     Conduction occurs due to transport of electrons
     Typically n-type conductors.
     Example: TiO2 , ZrO2 , CeO2 , Nb2 O5
    e) Metal Deficient Oxides
     Formation of either metal vacancies or oxygen interstitials (excess oxygen)
     Formation occurs typically at the surface.

    Following cases are possible:

    i) If metal deficiency is dominating defect then


     Depicted as metal deficient oxide M1-yO (y is the extent of non-
    stoichiometry)
     Possible defect reaction is that of electronic compensation
    1
    O2 ⇌ OO + VM′′ + 2ḣ
    2

     Creation of holes
     Conduction due to holes i.e. a p- type conductor
     Examples of oxides showing this characteristics are MnO, NiO, CoO, FeO
    etc.

    ii) If metal deficiency is dominating defect then


     Oxides depicted as MO2+x
     Oxygen interstitials can form due to following reaction
    1
    O2 ⇌ O′′
    i + 2h
    ̇
    2

     P-type conductor
     Example can be an oxide like UO2.
    Dissolution of foreign cations in an oxide
    a) Case-1: Parent oxide is MO and foreign oxide is Mf2O3.
    Following scenarios are likely:

    i. Mf3+ occupies M 2+ sites in MO giving rise to an extra positive charge on


    the metal site and a free electron according to following defect reaction
    1
    Mf2 O3 ⇌2 M ⦁fM +2OO + O2 ↑+2é (i)
    2
    ii. Alternatively for a metal deficient oxide MO, creates metal vacancies as

    Mf2 O3 ⇌ 2M ⦁fM + 3OO + VM


    ′′
    (ii)

    iii. For an oxygen deficient oxide, oxygen vacancies are compensated as


    VO•• + Mf 2O3 Û 2Mf• + 3OO (iii)
    M

    Reaction (iii) results is reduction in vacancy concentration, while


    reactions (i) & (ii) result in increase in the electron concentration or
    metal vacancy concentration.

    iv. Reaction (i), for a p-type conductor, can be alternatively expressed as


    following
    1
    2ḣ + Mf2 O3 ⇌ 2Mf⦁M + 2OO + O2 ↑ (iv)
    2

    b) Case-2: Parent oxide is MO and foreign oxide is Mf2O.


    It is recommended for the students to carry out this exercise.

    Summary
    In this lecture we have learnt about the existence of point defects as a reality in the materials and
    that their presence can be well studied using defects reactions similar to chemical reactions. The
    point defects can be neural as well as charged defects in most materials and they are denoted by
    Kroger-Vink notation. The guiding principle to form a point defect is that solid has to remain charge
    neutral. The point defect formation in a stoichiometric solid takes places by formation of cation and
    anion vacancies in stocihiomtetic amounts, called as Schottky defects or by formation of Frenkel (or
    anti-Frenkel) defects via formation of a vacancy of cation (or anion) and an interstitial of the same
    ion. On the other hand, in non-stoichiometric solids, defect formation also gives rise to a
    compensating electron or hole or oxidation or reduction for maintaining charge neutrality. We also
    looked at how impurities in the ionic solids can change their defect chemistry which can be used in a
    useful manner.

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