Chapter 1

Ceramic Structure
Instructor: Dong-Hau Kuo, Professor

Course: Electronic Ceramics

2022/02
Course Code: TX5410701; ME5412701
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,
John Wiley & Sons, 1990.
4. Dr. Patrick M. Woodward, Lectures of Solid State Chemistry, 1
Ohio State University
 Ceramic Bonding

Ionic bonding: metallic ions + nonmetallic ions

Cations Anions
Electric neutrality: e.g., CaF2, Al2O3, etc..

In reality, the atomic (non-metallic) bond between different

atoms has IONIC and COVALENT terms. A non-metallic
bond between dissimilar atoms can be described as a mixture
of ionic and covalent bond.
Both ionic and covalent bonding is classified as “strong”
bonding, and therefore most ceramics have high melting
point, are stiff, hard, and corrosion resistant. Both types of
bonds do not allow easy movement of dislocations under
stress, and therefore (unfortunately) ceramics are also brittle.

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 • (A -B) > 1.7 ionic bonding
• (A -B) < 1.7 covalent bonding
• According to Pauling, Ionic ratio PAB = 1- exp[-(A -B)2/4]

the calculation for KF (XK  1, XF  4) gives a maximum possible ionic character of ~ 92%, but
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for a "typical" ceramic, Al2O3, the maximum possible ionic character is only ~60%.
 r
EN   ( FA  FR )dr  E A  ER


a0

FA  FR  0 4
 e2  12 8 6 
 e2 MZ  Z  e 2
Ua   6     ....   M  
40 r  2 3 4

 40 r 40 r
N A MZ  Z  e 2
UA  
40 r
 12 8 6 
M   6     .... M= Madelung constant
 2 3 4 

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 Ionic Bonding

NaCl Formation of ionic bond

1. Mutual ionization occurs by electron transfer

2. Two ions are attracted by coulombic forces, but are

repulsive each other when separated at short distances.
N A MZ e Z e 
UA   U R  B/r n
4  o r

N A MZ  Z  e 2 B
U T  Molar lattice energy  U A  U R    n
4o r r

dU T N A MZ  Z  e 2 nB dU T
  n 1 ; 0 at r  ro
dr 4o r 2
r dr
nB N A MZ  Z  e 2 N A MZ  Z  e 2  r0n 1 N A MZ  Z  e 2  r0n 1
 B 
r0n 1 4o ro2 n  4o ro2 n  4o
N A MZ  Z  e 2 N A MZ  Z  e 2  r0n 1 N A MZ  Z  e 2  1
U T , min    1  n 
4o ro n  4o ro n
4o ro  
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The Born-Landé Equation
 The Born–Haber Cycle and Thermochemical Calculations

From Hess’ law:

The Born–Haber cycle and equation

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Cations are usually at
Tetrahedral and
octahedral sites

Anions Cations

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Interstitial sites in FCC

1. Octahedral sites : (0 0 ½ ), (0 ½ 0), (0 0 ½ ), ( ½ ½ ½ )

2. Size of octa. sites = (2-1) ro = 0.414 ro
3. Tetrahedral sites : ( ¼ ¼ ¼ ), ( ¾ ¾ ¾ ), ( ¼ ¼ ¾ ), ( ¼ ¾
¼ ), ( ¾ ¾ ¼ ), ( ¾ ¼ ¾ ), ( ¼ ¾ ¾ ), ( ¾ ¼ ¼ )
4. Size of tetra. sites = [(3/2)-1] ro = 0.225 ro

Interstitial sites in HCP

Interstitial sites in BCC

1. Only octahedral sites :

(0 ½ ½ ), ( ½ ½ 0), ( ½ 0 ½ )
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Figure 1.21 (a, b) Hexagonal unit cell of an hcp arrangement of spheres
showing (c) a threefold rotation axis, and (d) a 63 screw axis. 14
Pauling’s rules ：利用硬球模型替代離子並簡單地考慮靜電力作用
，以研究離子化合物穩定的幾何堆積
1. 陽離子被陰離子所形成的多面體所包圍，此陰離子的數量取決於
離子半徑比
2. Local charge neutrality：連結到氧離子的鍵結強度 (bond
strength)總和是+2，和氧離子的-2相匹配
3. 陰離子多面體(anion polyhedra)為了使彼此間斥力是最小，因
此多面體 3-D 堆積以分享 corner 優先，edge 次之，最不願的
是分享 face
4. 當陰離子多面體的配位數少，陽離子荷電高時，rule 3 就重要，
如 SiO2 以 corner 相連為主。
5. 多重陽離子的結構中，如果不同的陽離子之尺寸及電荷差異不
大，則呈現簡單的固溶體；差異大，陽離子可能採用不同的配位
數，產生較複雜的結構。

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electrostatic bond strength (ebs)

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Example:

Therefore, for an O that bridges two SiO4 tetrahedra, ebs = 2, which is, of
course, acceptable. However, three tetrahedra sharing a common O would give
ebs = 3 for that O, which is completely unacceptable.
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Factors on Bond length
(a) Bond valence

Al3+ and Si4+ cannot be distinguished by X-ray diffraction because of their very similar
scattering power, but in sites of similar CN they give different bvs; e.g. in regular MO4
tetrahedra, Si–O bonds have a bv of 1 but Al–O bonds have a bv of 0.75. Site occupancies
may therefore be determined using the valence sum rule and/or by comparing the M–O bond 29
lengths with values expected for Si–O and Al–O.
 Factors on Bond length
(b) d-electron: (i) crystal field effect

d-electron effect : crystal field theory (CFT)

P: Pairing energy
The energy difference,
: The energy difference, ,
, between t2g and eg
between t2g and eg orbitals
orbitals is set equal to
10 Dq
The magnitude of  depends on
the ligand or anion to which the
The eg orbitals in octa.
metal is bonded: for weak field
field are high energy
anions,  is small and the HS
orbitals (relative to t2g)
configuration occurs, and vice
since they point directly
versa for strong field ligands. 
towards the
also depends on the metal and, in
surrounding ligands
particular, to which row it
belongs: generally (5d) >
(4d) > (3d). Consequently HS
behaviour is rarely observed in
the 4d and 5d series.

Crystal field stabilisation

energy (CFSE):
6 × 4 Dq − 1 × 6 Dq = 18 Dq.
5 × 4 Dq − 2 × 6 Dq = 8 Dq
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 Factors on Bond length
(b) d-electron: (i) Crystal Field Effect

M2+ cation size: d-electron shielding effect  change bond length

• through Ca2+, Mn2+ (HS) and Zn2+. For these three ions, the distribution of d electron density is
spherically symmetrical because the d orbitals are either empty (Ca), singly occupied (Mn) or doubly
occupied (Zn). This decrease in radius is associated with poor shielding of the nuclear charge by the d
electrons short bond length. This trend continues in V2+, Cr2+ (LS), Mn2+ (LS) and Fe2+ (LS).
• On passing from V2+ to Cr2+ (HS) and Mn2+ (HS), electrons enter the eg orbitals, thereby shielding the
nuclear charge and giving an increased radius.
• Comparing Ti2+ with Ca2+, for instance, Ti2+ has an extra nuclear charge of +2 but the two extra
electrons in the t2g orbitals do not shield the bonding electrons from this extra charge. Hence, Ti–O
bonds in TiO are shorter than Ca–O bonds in CaO due to the stronger attraction between Ti2+ and the 31
bonding electrons.
Factors on Bond length
(b) d-electron: (ii) John-Teller distortions
In many transition metal compounds, the metal coordination is distorted octahedral and two axial bonds are
either shorter or longer than the other four bonds. The Jahn–Teller effect is responsible for these distortions
in d9, d7 (LS) and d4 (HS) ions.

The common coordination

environment of Cu2+ is
distorted octahedral with four
short and two long bonds.

Electrons in the doubly occupied orbital experience stronger repulsion and have higher energy than
electrons in the singly occupied orbital. This has the effect of lengthening the metal–ligand bonds in the
directions of the doubly occupied orbital, e.g. if the dz2 orbital is doubly occupied, the two metal–ligand
bonds along the z axis are longer than the other four metal–ligand bonds. Lengthening of the metal–ligand
bond along the z axis leads to a lowering of energy of the dz2 orbital.
High-spin d4 and low-spin d7 ions also have odd numbers of eg electrons and show Jahn–Teller distortions.32
Factors on Bond length
(b) d-electron: (iii) Square planar coordination

With increasing elongation along the z axis, however, a stage is reached where P < δ2, and the
doubly occupied dz2 orbital becomes stabilised and is the preferred ground state for a d8 ion.
The distortion from octahedral coordination may be sufficiently large that the coordination
becomes square planar as in tenorite, CuO (above); in many cases, e.g. PdO, there are no axial
ligands along z and, the transformation from octahedral to square planar coordination is
complete. Because they have no unpaired electrons, square planar compounds are
diamagnetic.

Filled orbitals
no bonding

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CsCl (Cesium Chloride) Structure

Lattice: Cubic - P (N.B. Primitive!)

Motif: Cl at (0,0,0); Cs at (1/2,1/2,1/2)

1CsCl in unit cell
Coordination: 8:8 (cubic)

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STRUCTURES DERIVED FROM
CUBIC CLOSE PACKING (CCP)

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 Rocksalt Structure O occupied; T+ and T− empty

• Cl-：FCC closed packing;

• Na+ ： all octahedral sites
• CN = (6,6)

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Rocksalt : NaCl、KCl、LiF、MgO、NiO、CoO、MnO、FeO、TiN、ZrN、BaO
Examples of Rocksalt Structure

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CCP Cl- with Na+ in all Octahedral holes
Lattice: fcc
Motif: Cl at (0,0,0)/4a; Na at (1/2,0,0) /4b
4NaCl in unit cell
Coordination: 6:6 (octahedral) 39
Cation and anion sites are topologically identical
The next three symbols denote symmetry elements
present in certain directions:

Crystal System Symmetry Direction

Primary Secondary Tertiary
Triclinic None

Monoclinic [010]

Orthorhombic [100] [010] [001]

Tetragonal [001] [100]/[010] [110]
Hexagonal/ [001] [100]/[010] [120]/[1(-1)0]
Trigonal
Cubic [100]/[010]/ [111] [110]
[001]

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 230 Space Group

Edge-sharing octahedra

the empty tetrahedral sites

Na (4b)
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Cl (4a)
Zincblende （Sphalerite）(閃鋅礦結構)
 Fcc-based structure
 ZnS、ZnTe、BeO、b-SiC、
 Anion：FCC closed-packing ; Cation：1/2 tetrahedral sites
 T+ (or T−) occupied; O, T− (or T+) empty
 Minimize the repulsion force
 Reduce Electrostatic Energy by keeping Zn as far apart as possible!
 Empty octahedral sites
 CN = (4,4)
 Derived Stgructure：Diamond cubic
Si, Ge, C
Zn (4c)
S (4a)

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Zn (4c)

S (4a)

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CCP S2- with Zn2+ in half tetrahedral holes (only T+ {or T-} filled)
Lattice: fcc
4ZnS in unit cell
Motif: S at (0,0,0); Zn at (1/4,1/4,1/4)
Coordination: 4:4 (tetrahedral)
Cation and anion sites are topologically identical 44
Examples of Zincblende （Sphalerite）(閃鋅礦結構)

zinc blende: T+ (or T−) occupied;

O, T− (or T+) empty

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 CaF2 (Fluorite, 螢石結構)

Fluorite
 CaF2, ZrO2、ThO2、CeO2、UO2
 Ca2+：FCC closed packing (8-f) ; F-：all tetrahedral sites
 Empty octahedral sites
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Ca, CN= 8

F, CN= 4

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Anti-fluorite (反螢石結構)
 K2O, K2S, Li2O, Na2O, Na2Se, Na2S
 O2-：FCC closed packing; Li+ ： all tetrahedral sites
 T+, T− occupied; O empty
 Empty octahedral sites

antifluorite: T+, T− occupied;

O empty.

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 Derivatives of Fluorite

Y2O3 = Y4O6 = Y4O8+2V

 Fcc-based structure
 Pyrochlore: Pb2Ru2O7、Bi2Ti2O7、Gd2Zr2O7
 Ordered oxygen vacancies => Good oxygen conductor

 SrCrF4 、 Sr2CuF6

(AX2)1 (AX2)2 (AX2)3

Examples of Fluorite & Antifluorite

ZrO2

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Ionic (and other) structures may be derived from
the occupation of interstitial sites in close-
packed arrangements.

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Dr S.J. Heyes