FUNDAMENTALS OF MATERIAL AND CORROSION PERFECT CRYSTAL 2

Perfect crystal Real crystal

CHAPTER 2: CRYSTALLOGRAPHIC DEFECT ✓ Contains no point, line, or ✓ Due to the effect of temperature,
planar defects (defect-free) particles can move (thermal
motion) and create defects.
✓ All particles are orderly
distributed to lattice points. ✓ Most crystals have a defect
Assoc. Prof. Dr. Nguyen Van Dung
content above 1%.
Faculty of Chemical Engineering, Ho Chi Minh City University of Technology, VNU-HCM ✓ Just an ideal case at 0 K
Email: nvdung@hcmut.edu.vn

CLASSIFICATION OF DEFECTS 3 CLASSIFICATION OF DEFECTS 4

By chemical composition: By impurity defect:

Stoichiometric defects: the ratio of cations to anions remains exactly Intrinsic defects: the presence of vacancies
the same as represented by the molecular formula. (missing atoms), interstitial atoms (added atoms),
or antisites (exchanged atoms for polar material)
Non-stoichiometric defects: defect anion and cations are not equal in
proportion. Extrinsic defects: are caused by the presence of
foreign atoms in the crystal structure.
Ex: NaCl & Na1+xCl, FeO & Fe1-xO with x ≪ 1
Ex: n-type semiconductor is Si doped with As
 CLASSIFICATION OF DEFECTS 5 CLASSIFICATION OF DEFECTS 6

By crystal lattice:
Point defects (0D)
Line defects (1D)
Planar or interfacial defects (2D)
Bulk or volume defects (3D)

Planar defects in SrTiO3

Line defects in Ti

POINT DEFECT 7 SYMBOLS AND ELECTRIC CHARGES 8

Stoichiometric defects: depend on ▪ MM is a M+ cation located in a correct M+ position.

temperature
▪ Mi is a M+ cation located in an interstitial position.
+ Frenkel defect
▪ XX is a X⁻ anion located in a correct X⁻ position.
+ Schottky defect ▪ Xi' is a X⁻ anion located in an interstitial position.
Non-stoichiometric defects: depend ▪ VM' is a vacancy of M+ cation.
on temperature and surroundings
▪ VX is a vacancy of X⁻ anion.
+ Impurity defects ▪ YM is a Y2+ cation located in a M+ position.
+ Non-stoichiometric defects ▪ LX' is a L2⁻ anion located in a X⁻ position.
 DEFECT RULES 9 STOICHIOMETRIC DEFECTS 10

➢ The main crystal lattice is not changed by defect. ❑ Frenkel defect: ❑ Schottky defect:
➢ The ratio of cation and anion lattice points does not change. A cation or anion moves into an An equal number of cations and
interstitial position, leaving an anions are missed from their
Ex: the ratio of Ca/F lattice points in the CaF2 structure is 1/2.
empty lattice position. lattice positions.
➢ The total positive charges are equal to the total negative charges.

➢ The numbers of elements and charges do not change in doping.

Ex: dope CaCl2 in NaCl crystal

CaCl2 → CaNa + 2ClCl + VNa'

FRENKEL DEFECT 11 SCHOTTKY DEFECT 12

Yakov Frenkel Walter Hans Schottky

(1894–1952), (1886-1976),
Russian physicist German physicist

For cation: Mi + VM’ = 0

VM’ + VX = 0
For anion: Xi’ + VX = 0
Ex: MgO, defects for O 2- Ex:
Oi’’ + VO = 0 + Defects in TiO2 crystals:
MgMg + OO = MgMg + Oi’’ + VO VTi’’’’ + 2VO = 0
+ Defects in BaTiO3 crystals:
VBa’’ + VTi’’’’ + 3VO = 0
 STOICHIOMETRIC DEFECTS 13 IMPURITY DEFECTS 14

Crystal Structure Defect Cation Y replaces cation M, or anion L replaces anion X (same valence).
Alkali halides (except Cs) NaCl Schottky
Ex: 1/ dope LiCl in NaCl crystal → LiNa
Alkaline-earth oxides NaCl Schottky
Caesium halides CsCl Schottky 2/ dope NaBr in NaCl crystal → Br Cl
BeO Wurtzite Schottky
AgCl, AgBr, AgI NaCl Frenkel (cation)
Alkaline earth fluoride, CeO2, ThO2 CaF2 Frenkel (anion)

IMPURITY DEFECTS 15 NON-STOICHIOMETRIC DEFECTS 16

Different valences (cation or anion) Case 1: Metal excess defect

Ex: introduce SrCl2 in NaCl crystal Create anion vacancies
+ Create vacancy: SrCl2 = SrNa· + ClCl + VNa' Ex: Na1+xCl, Zn1+xO with x ≪ 1
+ Insert into interstitial position: SrCl 2 = SrNa· + Cl i' + ClCl Heat ZnO: ZnO  Zn2+ + 1/2O2 + 2e-
Excess Zn2+ ions reside in the interstitial
positions, combining excess electrons
into Zn atoms.
 NON-STOICHIOMETRIC DEFECTS 17 NON-STOICHIOMETRIC DEFECTS 18

Case 2: Metal deficiency defect Case 2: Metal deficiency defect

+ Impurities + Metals with multiple valencies Heating FeO in air (O2) creates FexO (x <1).
Ex: add SrCl 2 into NaCl Ex: Fe1-xO, Ni1-xO with x « 1 Oxidation: FeO + O2 → Fe2O3; Fe2+ = Fe3+ + e
→ Na1-2xSr 2xVNa xO → Fe1-xO = Fe1-3x2+Fe2x3+VxO Excess electrons combine O2 to create O2-.
→ Fe1-xO = Fe1-3x2+Fe2x3+VxO

SOLID SOLUTION 19 SOLID SOLUTION 20

Include host atoms (solvent) and impurity atoms (solute)

The crystal structure of the solvent is unchanged by the presence
of the solute.
Solid solutions differ from liquid solutions and chemical
compounds.

Two types:
Substitutional solid solution: Solute atoms or ions replace solvent
ones.
Interstitial solid solution: Small solute atoms fill the empty spaces Substitutional solid solution Interstitial solid solution
between solvent atoms in a crystal lattice.
 SUBSTITUTIONAL SOLID SOLUTION 21 SUBSTITUTIONAL SOLID SOLUTION 22

Hume–Rothery rules:
Atomic size factor: the difference in atomic radii between the two
atom types is ±15%.
Similar crystal structure
Similar valence
Similar electronegativity
Ex:
The radii of Ca 2+ & Na+ are 1.04 & 0.98 Å, respectively.
→ Can create solid solutions (Ca 2+ in Na + or Na+ in Ca2+).
The radius of K+ is 1.33 Å, which is 40% higher than that of Na +.
→ Can create solid solutions at low temperatures.

MECHANISM FOR FORMING SOLID SOLUTION 23 INTERSTITIAL SOLID SOLUTION 24

Requirements:
The ionic solute has greater The ionic solute has lower
valence. valence. ✓ The atomic radius of the solute is small enough (rA/r B ≤ 0.59).
✓ Similar electronegativity and valence.
✓ Cation vacancy ✓ Anion vacancy ✓ Common solutes are H, N, C, B, and O.
Ex: NaCl doped with CaCl2 Ex: ZrO2 doped with ZnO + Carbide: TiC, ZrC, WC
→ Na1-2xCaxVxCl → Zr1-xZnxO2-x + Nitride: AlN, TiN, VN
Ex: FeC with rC = 0.71 Å < rFe = 1.24 Å.
✓ Interstitial anion ✓ Interstitial cation
Ex: CaF2 doped with YF3 Ex: Li4SiO4 doped with Al3+
→ Ca1-xYxF2+x → Li4+xSi1-xAlxO4
 EFFECTS OF DEFECTS 25 ELECTRICAL CONDUCTIVITY 26

The conductivity of metals depends on temperature.

Electrical As temperature increases, electron mobility is reduced by the thermal
properties
motion of electrons, and the resistance increases.

Catalytic Optical → Impurities and defects cause electron diffraction, increasing the
activity properties resistance

The electrical conductivity of semiconductors increases with

Defects increasing temperature. The number of electrons from the valence
bond can jump to the conduction band in semiconductors.
Mechanical Magnetic → Impurities in groups III (p-type semiconductor) and V (n-type
properties properties
semiconductor) make a lot more holes and free electrons, which
makes the semiconductor more conductive.
Thermal
properties Structural defects have little effect on the properties of the dielectric.

OPTICAL PROPERTIES 27 OTHER PROPERTIES 28

Absorption: The perfect crystals are transparent to light.
✓ Defects can create color centers.
✓ The absorption spectrum is influenced by the types of defects present.
✓ The absorption intensity depends on the defect content.
Radiation: When electrons move from the excited region to the valence
region, they emit light.
Fluorescence occurs mainly in crystals with impurities. Ex: KBr is
mixed with Tl 3+, ZnS; CdS is mixed with Ag+.
Thermal properties: heat capacity and thermal conductivity is little
affected.
Magnetic properties: Impurities C, S, N, and O strongly reduce the
magnetic permeability μ of ferromagnetic materials, reducing permanent
magnetism.
Mechanical properties:
+ Defects greatly reduce the mechanical strength of real crystals
compared to ideal crystals.
+ Impurities prevent the movement of lattice dislocations, increasing the
mechanical strength of the material.
Ex: steel from carbon atoms in iron structures

Catalytic performance: defect sites can become active sites. Vacancy

defects can donate or accept electrons, becoming catalytic oxidation-
reduction sites.
 THERMODYNAMICS OF DEFECTS 29 THERMODYNAMICS OF DEFECTS 30

For defect: ΔG = ΔH – T.ΔS Energy

ΔG: The change in the Gibbs free energy of the crystal lattice ΔH

ΔH: The energy required to create a defect

ΔS: The entropy change resulting from an increase in defects
ΔG
0
ΔG0 = -nE0F
E0 = - ΔH0/nF + T.ΔS0/nF
E0 = - a + bT

-T.ΔS
Measure E0 to determine thermodynamic parameters of defect.

Equilibrium position Defect content

ΔH & ΔS 31 DEFECT CONTENT FOR METALS 32

The total energy needed to create all defects: ΔH = nΔHf > 0

+ ΔHf: the energy required to create a defect
+ n: the number of defects Suppose that the crystal has N lattice points and n defects:
The entropy change resulting from defect formation: Use combination:
ΔS = k.lnW > 0
+ Boltzmann constant k = 1.38x10-23 J/atom.K
For 1 mole: R = 8.314 J/mol.K
+ W is the probability of defect formation
→ ΔG = nΔHf – k.T.lnW

At equilibrium position:
Apply this formula to calculate the defect contents of metals
 EFFECT OF TEMPERATURE 33 SCHOTTKY DEFECT FOR IONIC CRYSTALS 34

VM' + VX˙ = 0: n = cation defects = anion defects

Defect content:

The number of Schottky defects:

k = 1.38×10−23 J⋅K−1 for one species

R = 8.314 J⋅K−1⋅mol−1

As the temperature increases, the defect content increases rapidly.

SCHOTTKY DEFECT FOR IONIC CRYSTALS 35 FRENKEL DEFECT FOR IONIC CRYSTALS 36

Defect for cation: V'M + M˙i = 0

n vacancies at N lattice points
N = 8000 for 1000 unit cells
n interstitial defects at N* interstitial positions

3.1x10-14 Schottky defects

ΔS = k.lnW.W*
The number of Frenkel defects:
0.048 Schottky defects
nF = N .N *.e - H f /2 kT = N .N *.e -WF /2 kT
 FRENKEL DEFECT FOR IONIC CRYSTALS 37

Ex: Determine the defect contents in AgCl at 25 and 1000 oC.

AgCl: NaCl structure; Ag+ ions are defected.

For an unit cell: n

-N=4 = 2.e−WF /2kT
N
- N* = 8 = 2N
- At 298 K: 4.4.10-14
- At 1273 K: 9,7.10-4