Solid State Physics

Course no: PHY F341

2nd Sem (2019-20)

by
Subhashis Gangopadhyay
Department of Physics
(Room 3242-A)
 Elements

In general electron configuration not stable.

Electron configuration
1s 1
1s 2 (stable)
1s 22s 1
1s 22s 2
1s 22s 22p 1
1s 22s 22p 2
...
1s 22s 22p 6 (stable)
1s 22s 22p 63s 1
1s 22s 22p 63s 2
1s 22s 22p 63s 23p 1
...
1s 22s 22p 63s 23p 6 (stable)
...
1s 22s 22p 63s 23p 63d 10 4s 24p 6 (stable)
Valence (outer) shell usually not filled completely.
Atomic bonding: force and energy
 Inter-atomic bonding: Chemical and physical

Pimary (chemical): Secondary (physical)

van der Waals

Metallic bond (Metals) Induced dipole bond (Ar)

Ionic bonds (Ceramics) Permanent dipole bond

(HCl)
Covalent bonds
(Ceramics, Semiconductors) Hydrogen bond (H2O)
 Metallic bonds and structures
• valence electrons free to drift through entire material
• “Sea of electrons” surrounding net positive ionic cores
• non-directional bond

“sea of electrons”

+ + + +

+ + + +

+ + + +

+ + + +

ionic
cores
 Ionic bonding

• Occurs between + and - ions.

• Requires electron transfer.
• Large difference in electronegativity required.
• Example: NaCl
 Periodic tables

Electropositive elements: Electronegative elements:

Readily give up electrons Readily acquire electrons
to become + ions. to become - ions.
 Electro negativity

• Electro negativity ranges from 0.7 to 4.0,

Smaller electronegativity Larger electronegativity

 Ionic bonding

NaCl
MgO
H He
2.1 CaF2 -
Li Be O F Ne
1.0 1.5 CsCl 3.5 4.0 -
Na Mg Cl Ar
0.9 1.2 3.0 -
K Ca Ti Cr Fe Ni Zn As Br Kr
0.8 1.0 1.5 1.6 1.8 1.8 1.8 2.0 2.8 -
Rb Sr I Xe
0.8 1.0 2.5 -
Cs Ba At Rn
0.7 0.9 2.2 -
Fr Ra
0.7 0.9

Predominant bonding in many ceramics

 Covalent bonding

H2O

column IVA
H2 F2
C(diamond)
H He
2.1
SiC - Cl2
Li Be C O F Ne
1.0 1.5 2.5 2.0 4.0 -
Na Mg Si Cl Ar
0.9 1.2 1.8 3.0 -
K Ca Ti Cr Fe Ni Zn Ga Ge As Br Kr
0.8 1.0 1.5 1.6 1.8 1.8 1.8 1.6 1.8 2.0 2.8 -
Rb Sr Sn I Xe
0.8 1.0 1.8 2.5 -
Cs Ba Pb At Rn
0.7 0.9 1.8 2.2 -
Fr Ra
0.7 0.9 GaAs

Molecules with nonmetals, molecules with metals and nonmetals

Elemental solids and their compounds (RHS of Periodic Table)
 Covalent bonding

Requires shared electrons (CH4)

Electro-negativities are comparable

C: has 4 valence e,
needs 4 more
H: has 1 valence e,
needs 1 more
 Secondary (van der Waals) bonding
• Weaker than primary bonding
• Arises from electric dipole interaction
• Permanent or induced dipoles
• Hydrogen bond: highly polar molecule with H
Hydrogen bonding: melting of ice

Number of nearest neighbour molecules:

• Ice : 4
• Water: 4.5
 Ceramics: bonding and crystal structure

Ceramics: non metals, oxides and inorganic materials

Greek word Keramicos: burnt stuff, high temp treatment

Compound types: AX, AmBp, AmBnXp

Bonding type: Ionic, Covalent

(depends on magnitude of coulomb force)

Structure: Coordination number, ion position

(depends upon Cation to Anion size ratio)
 Ceramics: partial ionic bonding
Determined by materials electro-negativities
Percentage of ionic bonding (k) %

k = 100 {1-exp [- (0.25)(XA-XB)2 ]}

Stable bonding configuration
 Ionic radius

Element Ionic Atomic weight

radius (amu)
(nm)
chlorine 0.181 35.45
Oxygen 0.140 16
Sulfur 0.184 32.06
Calcium 0.100 40.08
Sodium 0.102 22.99
Barium 0.136 137.33
Titanium 0.068 47.87

Fluorine 0.133 19

Cesium 0.170 132.91

 Radius ratio rules

Coordination Ratio Structure

2 <0.155

3 0.155-0.225

4 0.225-0.414
 Radius ratio rules
Coordination Ratio Structure

6 0.414-0.732

8 0.732-1.0
 Radius ratio for coordination 3

Triangular planer structure

rc
 0.155
ra
 Radius ratio for coordination 4

Tetrahedral structure

r+ / r- = 0.225
 Radius ratio for coordination 6

Octahedral structure

r+ / r- = 0.414
 Radius ratio for coordination 8

Hexahedron structure

r+ / r- = 0.732
 Crystal structure of ceramics

AX types: rock salt (NaCl), zinc blend (ZnS, CuCl, SiC), CsCl

AmBptypes: CaF2, ZrO2

AmBnXp types: Perovskite (BaTiO3)

 AX type structure: NaCl (rock salt)

Na+ and Cl- both form FCC structure.

No of ions in unit cell = 8
No of molecule in unit cell = 4
Total lattice parameter = 2(rNa++rCl-)
Number of nearest neighbours = 6

Radius ratio 0.414-0.732

 NaCl: octahedral structure
Na and Cl ion sits at octahedral sites
No of octahedral sites = 4 Crystallographic points (Cl):
Na / Cl atom shifted at ½ 0 0 Corner atoms: 000, 001, 010, 100,
110, 101, 011, 111,
Face centered atoms: ½½0, ½½1,
½0½, ½1½, 0½½, 1½½
FC (- X UC): -½½0, -½½1, -½0½,
-½1½, -1½½
Shift by ½ along X (½ 0 0)
Corner: ½00, ½01, ½10, 1½00,
1½10, 1½01, ½11, 1½11
Face centered: 1½0, 1½1, 10½,
11½, ½½½, 1½½½,
FC (-ve X): 0½0, 0½1, 00½, 01½,
-½½½
Within unit cell: (Position of Na)
½00, ½01, ½10, ½11, 1½0, 1½1,
10½, 11½, ½½½, 0½0, 0½1, 00½,
01½
 AX type structure: CsCl

Cs+ and Cl- both form SC structure.

No of ions in unit cell = 2
No of molecule in unit cell = 1
Total lattice parameter = 2(rCs++ rCl-) /3
Number of nearest neighbours = 8

Radius ratio 0.732-1

 CsCl: hexahedron structure

Lattice is simple cubic,

Cs atom shifted at body centered ½ ½ ½
 AX type structure: ZnS (zinc blend)
Zn and S both form FCC structure.
No of atoms in unit cell = 8
No of molecule in unit cell = 4
Total lattice parameter = 4(rZn+ rS) /3
h
Number of nearest neighbours = 4
Highly covalent bonding

rc  ra  3a / 4
a
2ra 
2
rc
 0.225
ra
Radius ratio 0.225-0.414
 ZnS (zinc blend): Tetrahedral structure
Zn at tetrahedral site (¼ ¼ ¼) along body diagonal

Crystallographic points (S / Zn):

Corner atoms: 000, 001, 010, 100, 110, 101,
011, 111,
Face centered atoms: ½½0, ½½1, ½0½,
½1½, 0½½, 1½½,
Shift diagonally by ¼ (¼ ¼ ¼)
Corner: ¼¼¼, ¼¼1¼, ¼1¼¼, 1¼¼¼,
1¼1¼¼ , 1¼¼1¼, ¼1¼1¼, 1¼1¼1¼,
Face centered : ¾¾¼, ¾¾1¼, ¾¼¾, ¾1¼¾,
¼¾¾, 1¼¾¾
Within unit cell: (Position of Zn / S)
¼ ¼ ¼, ¾ ¾ ¼, ¾ ¼ ¾, ¼ ¾ ¾
 Fluorite Structure: CaF2

Alternate tetrahedral positions occupied by Ca++ ions.

All the tetrahedral sites are occupied by F- ions
Total 4 Ca++ and 8 F-

3
rCa    rF   a
4
 Perovskite Structure (BaTiO3)
• Bigger cation occupies corners
• Smaller cation at center of the cube
• Oxygen ion at faces
• Nearest neighbours are O-2 and Ti+4
a  2rO2  rTi  4 
Diamond structure

 Lattice → FCC
 Basis → two atoms: (0,0,0) & (¼, ¼, ¼)

 C, Si, Ge
 LATTICE = FCC
Basis: O(0,0,0) & T(¼, ¼, ¼)
Graphene structure
Carbon Nanotubes: structure
 FCC molecular crystal

C60 Fullerene crystal

Lattice parameter(s) a = 14.17 Å
C60 – C60 distance 10.02 Å
Volume of unit cell 711 Å3
 FCC VOIDS

TETRAHEDRAL OCTAHEDRAL

¼ way along body diagonal At body centre

{¼, ¼, ¼}, {¾, ¾, ¾} {½, ½, ½}
+ face centering translations + face centering translations
1
Vtetrahedron  Vcell 1
Voctahedron  Vcell
24 6
Note: Atoms are coloured differently but are the same
 Linear density

LD = No of atoms centered on a direction vector of unit length

FCC crystal along [110] = LD[110] = 1/2R

BCC crystal along [111] = LD[111] = 1/2R

 Planer density

PD = No of atoms centered on a plane of unit area

BCC crystal along (110) = PD(110)= 32/(16R2)

FCC crystal along (111) = D(111) = 1/(23R2)

 2
a
X2  Y 2
4
2
a
A sites a c/2 X2 
3
B sites a 2 2
c a
a2
 
A sites X a 4 3
Y
a c
 1.633
a
Predict crystal structures on the basis of ionic charge and ionic radii.

(a) For CaO, rCa2+ = 0.100 nm, rO2−= 0.140 nm, Ratio 0.713
Coordination number (Ca2+) is six, Predicted crystal structure is sodium chloride.

(b) For MnS, Radius ratio= 0.364

Coordination number is four, predicted crystal structure is zinc blende

(c) For KBr, Radius ratio= 0.704

Coordination number is six, predicted crystal structure is sodium chloride

(d) For CsBr, Radius ratio= 0.867

Coordination number is eight, predicted crystal structure is cesium chloride
 Atomic packing fraction of CsCl

Two ions are 0.170 nm and 0.181 nm

Ans. 0.684
Calculate the theoretical density of NiO
(a) Rock salt structure
(b) atomic radius of Ni+2 = 0.069 nm and O-2 =0.14 nm
(c) Atomic weight of Ni = 58.69 gm/mol, and for O = 16 gm/mol

Compute the theoretical density

Ans:
R = 6.79 gm/cm3
FeO
(a) Rock salt structure
(b) Density 5.7 gm/cm3
(c) Atomic weight of Fe = 55.85 gm/mol, and for O = 16 gm/mol

Determine the unit cell length

Compare with ionic radius data assuming Fe+2 and O-2 are just
touching along edge

Ans:
a = 0.437nm
atomic radius of Fe+2 = 0.077 nm and O-2 = 0.14 nm
a = 0.434nm
 Atomic packing in planes
(100) (110) (111)

SC

a
2a 2a

FCC a a

2a 2a

BCC

a
2a 2a
 Atomic planer density
SC FCC BCC
Atoms / Planer area Atoms / Planer area Atoms / Planer area
Area covered Area covered Area covered
(100) 1/a2 /4 = 0.785 2/a2 /4 = 0.785 1/a2 3/16 =
0.589
(110) 2/(2a2) 0.707(/4) = 2/a2 2/8 = 0.555 2/a2 32/16 =
0.555 0.833
(111) 1/(3a2) 0.577(/4) = 4/(3a2) /(23) =0.9068 1/(3a2) 3/16 =
0.453 0.34