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Chapter 2

Defects in Ionically Bonded Ceramics

Instructor: Dong-Hau Kuo, Professor
Course: Electronic Ceramics
2024/02
Course Code: TX5410701; ME5412701 ; ES5622701
National Taiwan University of Science and Technology

The contents comes from the following References:

1. Y.-M. Chiang, D. Birnie III and W.D. Kingery: Physical
Ceramics, John Wiley & Sons, 1997
2. A. R. West, Solid State Chemistry and its Applications, 2nd. John
Wiley & Sons, 2014.
3. L. L. Hench and J. K. West, Principles of Electronic Ceramics, ∗ + 𝐶𝑙∗ = 𝐴𝑔+ + 𝑉 − + 𝐶𝑙∗
− + 𝐴𝑔𝐴𝑔
John Wiley & Sons, 1990. ∗ + 𝐶𝑙∗ = 𝑁𝑎+
𝑁𝑎𝑁𝑎 𝐶𝑙 + 𝐶𝑙−𝑠 𝑢 𝑟 + 𝑉𝑁𝑎 + 𝑉𝐶𝑙 𝐶𝑙
∗ = 𝐴𝑔+ + 𝑉 −
𝑖 𝐴𝑔 𝐶𝑙
4. Dr. Patrick M. Woodward, Lectures of Solid State Chemistry, 1 𝐴𝑔𝐴𝑔 𝑖 𝐴𝑔
Ohio State University null = 𝑉𝑁𝑎
− 𝑠+ 𝑓+
𝑢 𝑟𝑉
𝐶𝑙

Defects in Ceramics
 Concentration of intrinsic defects：

 Frenkel defects：

 n/N = exp（-Gf/2kT）＝ exp（Sf/2k） exp（-Hf/2kT）

 G = Go + n Gf - T Sc

 Go：Free energy of Perfect ； Gf ：The formation energy of n Frenkel

defects (n vacancies + n interstitials) ； Sc : configuration entropy

 N!  N! 
Sc  k ln     2kN ln N  (N  n) ln( N  n)  n ln n 
 N  n i !n i ! N  n v ! n v!

利用n = ni = nv 及 ln N! = N ln N –N (Stirling approximation)

 G = Go + n Gf– 2kT [N ln N-(N-n) ln (N-n) – n ln n]
 ( G /n)T,P = 0 
n/N = exp（-Gf/2kT）＝ exp（Sf/2k） exp（-Hf/2kT）
(ni/(N-ni))(Nv/(N-nv) ~ (n/N)2 = exp (-Gf/kT)

3 n/N = exp（-Gf/2kT） 4
Chem. Rev. 2020, 120, 1710−1787

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Defects in Ceramics
Intrinsic defect concentration is affected by temperature
 Concentration of intrinsic defects：

 Schottky defects：

 （nv/N+nv）cat （nv/N+nv）an = exp（ -Gs/kT ）

 [Va] = [Vc] = exp（Ss/2k） exp（-Hs/2kT）

 H value can affect the defect concentration.

 Intrinsic defect concentration is affected by temperature, but it is not for extrinsic

defect concentration.

 Unit:

 n/N：atomic fraction; 1 ppm = a fraction of 106

 [Vca’’] ：number/unit volume

 molar fraction  no./volume by Na、 、 Mw

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Defects in Ceramics
Defect Formation Energy
 Kröger-Vink Notation：
 for the description of defects in ionic materials：
 main body：vacancy (V) or ion (M)
 subscript：host lattice sites or interstitials
 supercript：relative charge， 「+」  「 • 」， 「-」  「’」 ； 中
性
 「 x」
 VMg’’ ：the absence of an Mg2+ ion in MgO

 Ali•••：an insterstitial Al3+ ion

 FeMgx：Fe2+ substituted for Mg2+ in MgO

 FeMg•：Fe3+ substituted for Mg2+ in MgO

 FeFe•：Fe3+ substituted for Fe2+ in FeO

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Defects in Ceramics
 Intrinsic Defect Formation Equation：
 Schottky reactions for NaCl and MgO（intrinsic defects）


NaCl
 null＝ VNa’ + VCl• ，Ks = [VNa’] [VCl •] = exp（-Gs/kT）
MgO
 null＝ VMg’’ + V O• • ，K s = [VMg’’] [V O••] = exp（-G s’/kT）

 Frenkel reaction for AgCl （intrinsic defects）

AgCl
 AgAg x ＝ Ag i • + VAg ’ 

 F-centre defect: an electron trapped on an anion vacancy in halide system.

=1
Defect reactions of Al2O3 and BaTiO3 （intrinsic defects）
Al2O3
 null＝ 2VAl’’’ + 3V O••
BaTiO3
 null＝ VBa ’’ + VTi ’’’’ ＋3VO••

Defect chemical reactions can be happened if they obey the rules with the balance in mass,
lattice site, and charge.
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Defects in Ceramics
 Extrinsic defects：

Defects in Ceramics: Solid Solution  Substitutional solid solution，NiO in MgO （Isovalency substitution）
MgO
 NiO＝ NiMgx + O Ox
1. Substitutional solid solution
 Dissolution of Al2O3 in MgO（Heterovalency substitution）
MgO
a) (Al2−xCrx)O3: 0 ≤ x ≤ 2.  Al2O3 ＝ 2AlMg• + 3OOx Not favored with High H
3 MgO
 Al2O3 ＝ 2AlMg• + 3OOx + VMg’ favored
b) Mg2−xZnxSiO4, x<0.2
Al3+ and Mg2+ have the same coordination number of 6 and have close ion
c) LiCrO2 contains octahedral Cr3+ and forms solid solutions of formula: sizes.
LiCr1−xAlxO2  CaCl2 is added into NaCl
NaCl
2. Interstitial solid solutions  CaCl2 = Ca Na• + ClCl* + Cli’
2 NaCl
 CaCl2 = Ca Na• + 2 ClCl* + VNa’ 
a) Pd metal  an interstitial solid solution, PdHx: 0 ≤ x ≤ 0.7,
 YF3
CaF2
b) Interstitial sites for carbon in (a) α-Fe and (b) γ -Fe YF3 = Y Ca• + 2 FF* + Fi’  Ca1−xYxF 2+x
4+ 3+
 Ba1−xLaxTi1−x/4O3 or Ba1−xLaxTi1-xTixO3
 Bi2O3 added to BaTiO3: Bi2O3  2BiBa1+ + VBa2- + 3OO * 12
11
 BaTiO3 + LaFeO3 = (Ba,La)(Ti,Fe)O3  donor- acceptor codoping

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Defects in Ceramics
Defects in Ceramics
 Charge compensation reactions
 Extrinsic defects：
 Nb2O5 加入TiO2中
 Incorporation of MgO into Al2O3 （Heterovalency substitution）
1. ionic compensation mechanism
 Substitutional： 5 TiO2
Al2O3
 2MgO ＝ 2MgAl’ + 2O Ox + VO •• 2 Nb2O5 = 4 NbTi• + 10 O O* + VTi’’’’ Non-conductive
 Interstitial： 2. electronic compensation mechanism
Al2O3 4 TiO2
 3MgO ＝ 3Mgi•• + 3O x + 2V ’’’ 2 Nb2O5 = 4 NbTi• + 8 O O* + O2 (g) + 4e’ Electrically conductive
O Al

 Substitutional－Interstitial（self-compensating）： 3. （1）－（2）
Al2O3 * ’’’’
 3MgO ＝ 2MgAl’ + Mgi•• + 3O Ox O2 (g) + 4e’ = 2 OO + VTi Non-conductive
The third equation is favored for the high temperature reaction. Al3+and Mg2+ still
 Eq.（3）：High oxygen pressure favors the oxidation reaction and
have the different valencies for different defect formation energies.
executes the ionic compensation mechanism to form VTi’’’’ 。
 Double substitutions:
 Eq.（3）發現：Low oxygen pressure favors the reduction reaction and
executes the electronic compensation mechanism to form 4e’ 。

 For condition in between, partial ionic and partial electronic compensation

Add Al2O3 into Si3N4 to form S-Al-O-N 13 1 4
mechanism to have [Nb Ti• ] = n + 4[V Ti ’’’’] ---- Charge Balance Equatio n 。

Defects in Ceramics
Defects in Ceramics
 Extent of nonstoichiometry
 Oxidation and Reduction reactions
 Highly stoichiometric oxides： MgO、Al2O3、 SiO2、
 Reduction of oxides： O x ＝ 1/2O +V Electrically
2e’ O +
••
O 2 (g) conductive
Highly stable oxides are not easily oxidized or reduced to change its
 Equilibrium constant：kR = n2 ×[VO••] ×
PO21/2 ＝ kR’exp (-GR/kT)
stoichiometry. Even the change in oxygen pressure, the defect concentration of
oxides might not have a big change.
 Oxidation of oxides（VO•• elimination）：1/2 O2 (g) ＋ VO•• ＝ OOx + 2 h• Electrically
conductive
 Equilibrium constant：kO = p2 / [VO••] ×
PO21/2 ＝ kO’exp (-GO/kT)  Highly nonstoichiometric oxides：
TiO2-x；BaTiO3-x、SrTiO3-x：Have the transition metals with multivalency ,
 Oxidation reaction ＋ Schottky reaction： 1/2 O2 (g) ＝ OOx ＋VMg’’ + 2 h• Electrically
conductive Ti4+ to occur Ti4+ Ti3+
 the above result ＋ [null = e’ + h• ]： 1/2 O2 (g) ＋2e’＝ OO x+ VMg ’’ Non-conductive
 Ni1-xO（x = 5×10-4；Ni2+ Ni3+）； Co1-xO（x = ~0.01；Co2+ Co3+）；
The above equations exist some interconnection. Which equation is important is Mn1-xO（x = ~0.1；Mn2+ Mn3+ or Mn4+）； Fe1-xO（x = ~0.15；Fe2+
determined by the facts from characterizations. For example, a metal with a high Fe3+） 3FeO
FeFe* = 2FeFe+ + VFe2-
vapor pressure, then the reaction equation should be written as:
 ZrO2-x、
MMO(s) = M(g) instead of OMO(s) = ½O2 (g)。 • Mei type compounds include: Zn1+xO, Cr2+xO3, Cd1+xO
• Vx type compounds include: ZrO2-x, TiO2-x
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Fe1-xO
Nonstoichiometry and Defects in LiNbO3

• Fe1−xO would have the structural formula Fe2+ 1−3xFe3+2x VxO in which Fe2+, Fe3+ and  Mg1−3xAl2+2xO4; Li2−4xTi1+xO3: 0 < x <∼ 0.19
cation vacancies were distributed at random over the octahedral sites in the ccp oxide  From phase diagram of LiNbO3，There is a wide range of stable nonstoichiometric
ion array. Fe1−xO is a p-type semiconductor. compositions with a solid solution with Nb in rich 。 What kinds of defects in this material
• The defect structure is different, however, since neutron and X-ray diffraction studies to form Nb-rich Solid solution?
have shown that Fe3+ ions are in tetrahedral sites and that defect clusters appear to Evidence：exist NbLi•••• defect or the Nb
form. occupies the Li lattice to form antisite。 Nb/Li > 1
Antisite defects easily occur in multication
oxides 。

NbLi•••• need to have VLi’ for charge

compensation with ：[VLi’] = 4 [NbLi••••] ,
because the lower formation energy of the VLi’
＋Lii• Frenkel defects 。Single crystal
experiments observe：the existence of VNb’’’’’＋
NbLi••••，and form (VNb’’’’’＋ NbLi••••)‘ associates。

𝐿𝑖𝑁𝑏𝑂
𝐿𝑖 ∗ + 𝑁𝑏∗ 3
•••• + 𝑉 ′ ′ ′ ′ + 𝐿𝑖 •
𝑁𝑏𝐿𝑖
𝐿𝑖 𝑁𝑏 𝑁𝑏 𝑖

17 𝐿𝑖𝑁𝑏𝑂3 18
∗ + 𝑁𝑏 ∗ + 𝑉𝐿
𝐿𝑖𝐿𝑖 𝑁𝑏 ′
𝑁𝑏•••• + 𝑉 ′′′′
𝑖 𝐿𝑖 𝑁𝑏

Sn added to IGZO (InGaZnO4), [InGa(Zn1-xSnx)O4

Suppose to be : the increased

Electronic compensation content of Sn4+ substitute leads to
the higher positive charge
• Cation vacancies may be generated by deintercalation, as in removal of Li+ (and e−) from
materials such as LiCoO2 and LiMn2O4.
concentration. It favors to
• Insulating NiO, which oxidises and becomes black and semiconducting on heating to increase the negative charge
form Ni1-xO: concentration or form the metal
vacancies to lower the positive
• YBa2Cu3Oδ, for Cu charge states:
charge content in order to keep
(a) δ = 6, 1+ & 2+, semiconductor; (b) δ = 6.5, 2+; (c) δ = 7, 2+ & 3+; Superconductor the charge neutrality.
(d) δ = 6 : O interstitial totally empty  δ = 7 : Oxygen interstitail totally filled. Analytic Phenomenon : the
• Li intercalation:
electrical conductivity increased,
• Ba-doped La2CuO4 : the lattice oxygen content
• BaBiO3 : decreased, and the oxygen
vacancy content increased with
• Experimental methods for studying solid solutions
(a) X-ray powder diffraction, XRD; (b) Density measurements; (c) Changes in other
the increase in the Sn
properties – thermal activity and DTA/DSC, Electrical property concentration.

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InGaZnO4
For transparent IGZO Oxidation of Fe3O4 Spinel by N2O or O2 into -Fe2O3
MOS transistor
device
InGaZnO4

IGZO to Sb-IGZO

2+
[VO ] drop A general formula for the oxidation

ZnOS
Dy-ZnOS
At = 1, the spinel becomes the -Fe2O3 with the same structure of
Mn2+-deficient spinel
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Defects in Ceramics
Defects formed by the gas-oxide reaction
 MgO as an example Electron/Hole
Formation
Defect Formation
(1) H2S or NH3 reacts with oxide
Major defect：Schottky defects 、Schottky formation energy of Hs  7.7
eV、 Band gap of Eg  7.65 eV（25 oC）、Hard to form the intrinsic
defects、easily to form the extrinsic defects with impurity.

Intrinsic defect at 1400 oC：me* = 0.38 mo，mh*= 0.77 mo，mo= 9.11 

10-31 kg，k = 1.38  10-23 (J/k) ，h = 6.63  10-34 (J-sec) ，MWMgO= 40.3
g/mol，DMgO = 3.58 g/cm3

    K1/2  exp   Hs   2.5 10 12

[V ''Mg]  V O s  molar fraction
 2kT 
(2) H2 or H2O reacts with oxide 3/2
i  NcN v
n  p  K1/2 1/2 exp  Eg    2 kT   m*
 2kT   2h2 


 1.3 1020   7.65
cm 3 exp 
e


V'M' g V 

 MgO has extremely low defect concentration.
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Defects in Ceramics Defect Dipoles

Donors and Acceptors：all ionic defects with nonzero effective charges can be (-) (+)
viewed as donors or acceptors
 Donor level：for energy level before ionization
1. Defects with a positive effective charge, VO••、VO•，given up an electron
in order to become ionized positively
2. Energy level is labeled with the charge state before ionization
3. As5+、P5+、Sb5+ in Si。As (metal) = AsSi• + e’
 Acceptor level：For energy level after ionization
(+) (-)
1. Defects with a negative effective charge having accepted electrons relative
to the perfect lattice
2. Energy level is labeled with charge state after ionization
3. B3+、Al3+ in Si。B (metal) = BSi’+ h•

 Donors：positively charged defects

 AlMg•、ClO• 、V O•• in MgO Donor and Acceptor Levels
 Acceptors：negatively charged defects for selected dopants in silicon (+)
 NaMg ’、NO ’ 、VMg ’’in MgO (-)

in TiO2
 Donors：NbTi•、TaTi• 、VO •• 、Tii ••••
 Acceptors：AlTi’、GaTi’ 、VTi’’’’、Oi’’
 in BaTiO3
 Donors：LaBa•、YBa•
 Acceptors：AlTi’、FeTi’ 、YTi’
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Chem. Rev. 2020, 120, 1710−1787

Acceptor- and Donor-codoped BaTiO3

Defect Characterizations in Nd3+-doped BaTiO3
(Ba1-xNdx)TiO3
1. Ba(Ti4+,Al3+,Nb5+)O3

Defect Associate
2. (Ba2+,Bi3+)(Ti4+,Mn2+/3+)O3

 Ba Vacancies & Oxygen Vacancies

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Chem. Rev. 2020, 120, 1710−1787

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Defects in Ceramics
Reducible Oxides
 Special Topic：CaO-doped ZrO2-x  n-type Semiconductors

After pure ZrO2 is sintered at high temperature, it

will be dusting during cooling due to the cubic  TiO2, CeO2, ZrO2,
tetragonal  monoclinic phase transformation 。
CaO doping can stop this phase transformation to V2O5, FeO, PrO2,
hold the high temperature phase at low temperature SmO, CoO, MnO,
to form as the metastable phase。 V2O5, MoO3, and
 CaO-doped ZrO2 forms VO •• to balance the defect WO3 et al.
equation. It has good O2- ionic conduction and can
be used for O ion-transport solid electrolytes。 more complex
 Defect reactions solids,
 CaO(s)  CaZr’’ + OO *+ VO •• such as the
Zr1−xCaxO2−x , 0.1 < x < 0.2 BaTiO3, LaCoO3,
 2 CaO(s) + ZrZr* 2 CaZr’’ + 2 OO *+Zri ••••
and HfSiO4

Both equations lead to different density values.

You can use pycnometer for density and XRD for
lattice parameter to determine the kind of defects.
For example, if density becomes smaller and the
lattice becomes smaller, then the first equation is La3+, Nd3+, Sm3+/2+, Tb3+/4+, Dy3+, Tm3+/2+
29 30
preferred.

Confirmation of Oxygen Vacancies in CeO2

STM image STM image
Spectrum of XPS O1s and
the effect of copper doping
on ceria.

Internal Compression to
However, when a vacancy is Vacancy Dimerization: When Inhibit the crack propagation.
typically formed, it exposes two dimerizing, these clusters of
Ce3+ atoms and one Ce4+ atom that is vacancies expose only reduced
smaller than Ce3+. metal atoms without distortions
in the crystalline lattice and are,
therefore, thermodynamically t m phase transformation
more favorable.  Compression zone
 Stop the crack propagation
31  Toughening 32
Ce4+ has four CeO bonds on a plane

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Defects in Ceramics Experimental determination of defect type

The measurement of lattice parameter and density
 Special Topic：CaO-doped ZrO2

For CaO-added ZrO : 2 Case  Ca Zr  O O  V O

ZrO2
A : CaO 
''  

Case ZrO2 

r(Ca2+) = 100 pm B : 2CaO  ZrO 2  2 Ca 
i  Zr i  OO

r(Zr4+) = 72 pm
 Determined from XRD => Fluorite structure; a = 5.131Å ； 4 ZrO2/unit cell
For Zr 0.85 Ca0.15 O 1.85,
Case A; oxygen vacancy do min ate Case B; Interstiti als do min ate
40.08 Zr0.85Ca0.15O1.85  Zr0.92Ca0.16O2
Ca :  4 0.15
NA 40.08
Ca :  4 0.16 
91.22 NA
Zr :  4 0.85
NA 91.22
Zr :  4 0.92 
16 NA
O:  41.85
NA 16
O:  4 2 
 CaO(s)  CaZr’’ + OO *+ VO  CaO(s)  CaZr’’ + OO *+ VO M M Ca  M Zr M O NA
•• ••
   5.57g/ cm3 
 6.01g/ cm3
V  8 3 M M Ca  M Zr M O
 Quench at 1600 oC ，lead to VO •• defect.  2 CaO(s) + ZrZr*  2 CaZr’’ + 2 OO *+Zri •••• 5.13110    3
  V 
5.131108 
 

 Quench at 1800 oC ，the defects change from cation interstitial Zri• • • •  The experimental result for density is 5.57 g/cm3 => oxygen vacancies dominate 34
to VO••, as the CaO doping content is increased. 33
ZrO2 theoretical density = 5.68 g/cm3

Defects with Crystallographic shear structures

1. certain transition metal oxides could be prepared with an
apparent wide range of non-stoichiometry, e.g. tungsten
bronze WO3−x, MoO3−x, TiO2−x, VO2-x.
2. In oxygen-deficient rutile, a homologous series of phases
occurs of formula TinO2n−1 with n = 3–10.相同結構的 P-type Semiconductors
[Link] vanadium dioxides, VnO2n−1: 4 ≤ n ≤ 8,
4. WO3-x as an example of ReO3 structure: Such a structure
would, of course, be unstable and so a partial collapse occurs
to eliminate the layer of vacancies and form the CS planes
with Wadsley CS defects: WnO3n−1: n = 8
CS: Crystallographic Shear

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1. Perovskites
a) (La,Sr)BO3, B= V, Cr, Co
b) K-BaSnO3, Ba(Zr,Ga)O3, Sr(Ti,Sc)O3, (La,Sr)RhO3

2. Cu+-based oxides
a) CuMO2, M= Al, Ga, In
b) SrCu2O2 Defects for Colors from Ceramics
3. Layered oxychalcogenides
a) LaCuOS (CuS alyer + LaO layer)
b) (La,Sr)CuOS

4. d6 spinel oxides:
ZnRh2O4, InGaZn2O4 (IGZO)

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Defects in Ceramics

 Special Topic：Color and color centers

 Blue sapphire (藍寶石) Coloring

 Fe、Ti co-doping into Al2O3 。

2 Al
 Fe  Fe2+ ， Fe3+； Ti  Ti4+ ， Ti3+
 Composition, temperature, and oxygen pressure need to be controlled.
2 Al
 Fe + Ti  FeAl’ + TiAl•
Ceramic Colors from
Strong absorption at the red light region with electrons jumping around
d Orbital Degeneration
the neighboring cations.

 Show the complementary color of blue color.

 Charge transfer color（電荷移轉呈色）

h
 Mechanism： Fe2+ + Ti4+  Fe3+ + Ti3+

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Effects of the metal oxidation state and of ligand strength on color The electronic spectrum of [Ni(H2O)6]2+:

The complex looks green, because it absorbs only weakly at 500 nm,
the wavelength of green light. It absorbs in the red region 620-750 nm which is the
complimentary color of green

UV visible infrared
[V(H2O)6]2+ [V(H2O)6]3+

[Ni(H2O)6]2+


560 nm green
460 nm
17900 cm-1 21700 cm-1

red

540 nm [Cr(NH3)6]3+ 460 nm

[Cr(NH3)5Cl ]2+ 18500 cm-1 41 λ, 42
21700 cm-1

Visualization of color as transmitted light which is not absorbed

Gem Stones : Ruby and Emerald d Orbitals in Crystal Field from the Ligands
in octahedral field

corundum (Al2O3) and Ruby: corundum with

chromium as impurity.

Mineral beryl (Be3Al2(SiO3)6), and Emerald: Beryl

colored green by trace amounts of chromium and/ or
vanadium
In real systems there are regions of different light absorptions leading to a wide range of colors. Strong
transmission can dominate a weak transmission.
43 44

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d Orbitals in Crystal Field from the Ligands d Orbitals in Crystal Field from the Ligands

in octahedral field in octahedral field

(2S+1)F , J= L+S or L-S

J

Spin degeneracy=
2S+1 = 4

45 46

47 48

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This rule affects Octahedral and

Spin Selection Rule Square planar complexes as Cr3+ Gemstones
they have center of symmetry.
Allowed
Statement : This rule states that transitions that involve a change g u & u g
in spin multiplicity are forbidden. According to this rule, any
transition for which  S = 0 is allowed and  S  0 is forbidden Not allowed (FORBIDDEN)
g g & u u

Practical significance of the Spin Selection rule

Tetrahedral complexes do not
During an electronic transition, the electron should not change
have center of symmetry:
its spin
therefore this rule does not
apply.

d5 High spin (e.g

[Mn(H2O)6]2+

eg eg
h

[GS] [ES] [GS] [ES] t2

t2
g
S = 0 S  0 g
S  0 Forbidden
Allowed Forbidden
49
There are three mechanisms that allow ‘forbidden’ electronic transitions to become somewhat ‘allowed’resulting in Absorption 50
some intensity of the color expected. (1) Vibronic Coupling, (2) Mixing of states, (3) Spin orbit coupling. in green- Absorption in
yellow yellow-red

for a d3 configuration:
Tunabe-Sugano Diagram Cr3+ Total value of L = +2 +1+0 = 3 F term symbol.
Total S = 3/2 , 2S+1 = 4
4F

52

51

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Defects in Ceramics Defects in Ceramics

 Interaction between point defects and interface  Interaction between defects and interface－ Intrinsic potential
Frenkel defects can be formed inside, but Schottky defects need  Schottky defects for MgO
MgMg* = V Mg’’ + Mg surf •• gVMg Ks1 = [Mgsurf ••][V Mg’’] Surface Charge
space for ions to stay like at surface, grain boundary, dislocations 。 Metal rich
 Ionic space charge：For Schottky defects，to view VMg’’ and V •• OO* = V O •• + Osurf ’’ gVO Ks2 = [Osurf ’’][V O ••]
O
independently occur： MgMg* ＋OO* = Mg surf •• ＋ Osurf ’’ ＋ VMg’’ ＋ VO ••
Metal-less, VM-rich
null = V Mg’’ ＋ VO •• ； Ks = [V ’’] [V ••] Space Charge
Mg O
MgMg* = VMg’’ + Mgsurf•• gVMg layer
 if gVMg ＜ gVO  Mgsurf •• rich on surface  [VMg’’] lower  [V O ••]
* •• ’’
OO = VO + Osurf gVO higher  [Osurf’’] lower  Osurf’’ lower on surface。

Schottky energy： gs = gVMg + gVO  Defect concentration in the space charge layer follows the spatially-
varying potential to change with distance. definition： (x) = 0 at
 Ionic space charge：For Frenkel defects ，two steps to form: (1) surface；  (x) =  in the bulk。
ions move to surface or interface to leave vacancies in lattice，gV， V ''M g x   e xp   g VM gk T 2 e  ( x )  V O  x   e xp   g VO kT2 e  ( x ) 
   
(2) surface ions move to the interstial sites， gi。Frenkel energy = gf
= gv + gi。  Deep-inside MgO will not be affected by the space charge zone.
 Each defect has its own formation energy to make surface defect [VMg’’] = [V O ••] g  2e  VMg   g Vo  2e 

concentration different from the defect energy in lattice. Therefore, kT kT

there is a net charge at surface, which is balanced by the space

e  
1
4
 
g VMg  g Vo  0

charge inside the crystal with a gradually decreased concentration For surface area and space charge area, there is a potential difference
53 of [gVMg - gVo], if surface potential is zero, the space charge area has 54
gradient. negative potential:  < 0。

Defects in Ceramics  Interaction between defects and interface－Rutile TiO2-x

 Interaction between defects and interface－ Extrinsic defect
 Surface charge is originated from the charge balance between the (1)TiO2-x ：VO •• together with some
surface ions and the inner defects. If the inner defects change, the Tii••••。At high temperature， Tii••••
outer surface potential will also alter. 。 moves to boundary to from cation-
 For Al-doped MgO ；MgO has Schottky defects （[V Mg’’] and rich G.B. , let to  < 0 ，i.e. a
[V ••]）。For the requirement of charge balance： negative space-charge potential。
O

[AlMg•] + 2 [VO••] = 2 [V Mg’’]

(2) Acceptor-doped TiO2-x：
 increase Al dopant，increase [V ’’]， decrease [V ••] 。
Mg O AlTi’ defects to choose Tii••••for
 increase [V ’’]，decrease [Mg ••] ，increase [O ’’] 。 ＋ charge compensation。The same as
Mg

surface has more anions   ＞ 0

surf surf
＋ un-doped TiO2-x，  < 0 ，i.e.

＋ form a negative space-charge


Definition： (x) = 0 at surface；  (x) =  in the bulk。  ＞ 0 。
at r =  ，low [VO ••]
＋ potential ， G.B. is rich in Tii••••。
＋
 [VMg ’’]  ½ [AlMg •] = exp [(-gVMg + 2e)/kT]
Surface ＋
(3) Donor-doped TiO2-x：as
Space doped with Nb2O5（NbTi•），form
 kT (ln(1/2) + ln [AlMg •]) = -gVMg + 2e charge － charge VTi at lattice for charge
’’’’

 e = (½ )gVMg + ½ kT ln [AlMg •] － ½ kT ln(1/2) > 0 － compensation。Need [NbTi•] = 4

 gVMg > 0 and [AlMg •] > 0 － [VTi’’’’]，as Nb2O5 increases， [VTi’’’’]
－
••••
increases，[Tisurf ] decreases，
 intrinsic（  < 0 ）/extrinsic（  ＞ 0 ）  reach  = 0
isoelectric point － [Osurf’’] increases  surface（G.B.）
with negative charge   > 0 ，i.e.
－ form a positive space-charge
55 56
potential 。

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Positive & negative charge segregation are related to the total Anion defects in transition metal oxides
dopants, temperature, and oxygen pressure
Oxygen-deficient Perovskite Ca—Nd2MgTiO6-d Nd1.9Ca0.1MgTiO6-d
according to the Kröger–Vink notation the mechanism can be described as in eqn (1):

Nd1.90Ca0.10MgTiO6−δ shows up to 14% of anti-site (AS) defects as Mg and Ti partially share B′ and
B″ sites.
O removal
Perovskite ------ Rocksalt-like Structure

(V••
O-Ca′Nd)

Nd2MgTiO 6 Nd1.9Ca0.1MgTiO6-d
Inducing oxygen vacancies with acceptor dopants can in fact
result in the trapping of these oxygen vacancies eV•• O through
the attractive electrostatic interactions between the positively
Perovskite Perovskite with charged anion vacancies and the negatively charged aliovalent
cations Ca′Nd.
57 only B-site Rocksalt- A-site and B-site Rocksalt- 58
like ordering like ordering

Anion defects in transition metal oxides

to modify the electronic Structures

eg LaCoO3 Fe-doped
LaCoO3
t2g

59
S doping in CaMnO3 Zn doping in Co3+OOH J. Mater. Chem. A, 2019, 7, 5875–5897

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