CRYSTAL

STRUCTURES
Matter what is available in nature can be
classified into three STATES

GASEEOUS

LIQUID

SOLID
 SOLID
 CRYSTALLINE  AMORPHOUS
SOLID SOLID
SOLID IN WHICH ATOMS ARE ARRANGED IN REGULAR

MANNER WITH PERFECT PERIODICITY OVER A

LONG RANGE ORDER, ARE CALLED CRYSTALLINE SOLID

ATOMS ARRANGED IN IRREGULAR MANNER,

CALLED NON-CRYSTALLINE SOLID

 CRYSTAL STRUCTURE
 Crystal structure can be obtained by attaching atoms,
groups of atoms or molecules which are called basis (motif)
to the lattice sides of the lattice point.
Crystal Structure = Crystal Lattice + Basis
THE REGULAR ARRANGEMENT OF POINTS
INSTEAD OF ATOMS IS CALLED LATTICE.
IT IS AN IMAGINARY CONCEPT
Eg: egg box

A GROUP OF ATOMS OR MOLECULE ATTACHED TO EACH

LATTICE POINT WHICH ARE IDENTICAL IN COMPOSITION
AND ORIENTATION IS CALLED BASIS
Eg: EGGS
 CRYSTAL STRUCTURE

 Don't mix up atoms with

lattice points

Crystal Structure
 Lattice points are
infinitesimal points in space
 Lattice points do not
necessarily lie at the centre
of atoms

Crystal Structure = Crystal Lattice + Basis

 UNIT CELL
IT IS A BUILDING BLOCK OF CRYSTAL STRUCTURE

IT IS A MINIMUM NUMBER OF ATOMS

BY THE REPETATION OF IT IN THREE DIMENSION
WE CAN CONSTRUCT THE TOTAL CRYSTAL STRUCTURE
Unit Cell  The unit cell and, consequently,
the entire lattice, is uniquely
determined by the six lattice
constants: a, b, c, α, β and γ.
These are lattice parameters

 a, b, c are axial lengths; α, β and

γ. Interfacial angles
DEPEND UPON THE LATTICE PARAMETER CRYSTAL SYSTM
CAN BE CLASSIFIED INTO SEVEN SYSTEMS THOSE ARE

1.Cubic Crystal System (SC, BCC,FCC)

2.Hexagonal Crystal System (S)
3.Triclinic Crystal System (S)
4.Monoclinic Crystal System (S, Base-C)

5. Orthorhombic Crystal System (S, Base-C, BC,

FC)
6. Tetragonal Crystal System (S, BC)
7. Trigonal (Rhombohedral) Crystal System (S)
Cubic Crystals
a = b= c
 =  =  = 90º

• Simple Cubic (P) - SC

• Body Centred Cubic (I) – BCC SC, BCC, FCC are lattices
• Face Centred Cubic (F) - FCC while HCP & DC are crystals!

 Elements with Cubic structure → SC: F, O, Po ||

BCC: Cr, Fe, Nb, K, W, V||
FCC: Al, Ar, Pb, Ni, Pd, Pt, Ge
Tetragonal Crystals
a=bc
 =  =  = 90º

 Simple Tetragonal
 Body Centred Tetragonal -BCT

 Elements with Tetragonal structure → In, Sn

Crystal Structure
Orthorhombic Crystals
abc
 =  =  = 90º

 Simple Orthorhombic
 Body Centred Orthorhombic
 Face Centred Orthorhombic
 End Centred Orthorhombic

 Elements with Orthorhombic structure → Br,

Cl, Ga, I, Su
Monoclinic Crystals
abc
 =  = 90º  

 Simple Monoclinic
 End Centred (base centered) Monoclinic
(A/C)

 Elements with Monoclinic structure → P, Pu, Po

Triclinic Crystals
abc
  

• Simple Triclinic

Crystal Structure
 Trigonal/Rhombohedral
Crystals
a=b=c
 =  =   90º

• Rhombohedral (simple)

 Elements with Trigonal structure → As, B, Bi, Hg, Sb, Sm

Crystal Structure
Hexagonal Crystals
a=bc
 =  = 90º  = 120º

 Simple Hexagonal

Crystal Structure
 Elements with Hexagonal structure → Be, Cd, Co, Ti, Zn
Auguste Bravais LATTICES
(1811-1863)

 In 1848, Auguste Bravais demonstrated

Crystal Structure
that in a 3-dimensional system there are
fourteen possible lattices
 A Bravais lattice is an infinite array of
discrete points with identical
environment
 seven crystal systems + four lattice
centering types = 14 Bravais lattices
 Lattices are characterized by translation
symmetry
 Crystal Structure

simple cubic body-centered cubic face centered cubic

BASE CENTERED
 Examples of elements with Cubic Crystal Structure

Fe Cu
Po

n=2 BCC n = 4 FCC/CCP

n=1 SC

n=8 DC
C (diamond)
Properties of unit cell

1. Coordination Number
2. No of Atoms Per Unit Cell
3. Lattice Constant
Atomic Radius
Atomic Packing Fraction
No of Atoms Per Unit Cell
Effective no of atoms per unit cell
 COORDINATION NUMBER

 Coordinatıon Number (CN) : The Bravais lattice points closest

to a given point are the nearest neighbours.

Crystal Structure
 Because the Bravais lattice is periodic, all points have the same
number of nearest neighbours or coordination number. It is a
property of the lattice.

 A simple cubic has coordination number 6;

 A body-centered cubic lattice, 8;
 A face-centered cubic lattice, 12.
ATOMIC PACKING FACTOR

 Atomic Packing Factor (APF) is defined as the

volume of atoms within the unit cell divided
by the volume of the unit cell.
 1-CUBIC CRYSTAL SYSTEM
a- Simple Cubic (SC)
 Simple Cubic has one lattice point so its primitive cell.

Crystal Structure
 In the unit cell on the left, the atoms at the corners are cut
because only a portion (in this case 1/8) belongs to that
cell. The rest of the atom belongs to neighboring cells.
 Coordinatination number of simple cubic is 6.

b
c

a
SIMPLE CUBIC STRUCTURE (SC)

• Rare due to low packing density (only Po has this structure)

• Close-packed directions are cube edges.

• Coordination # = 6

Crystal Structure
(# nearest neighbors)
SHARING OF CORNER ATOM WITH EIGHT
NEIGHBOURING
UNIT CELLS
 NUMBER OF ATOM PER UNIT CELL

Fe
Po

n=2 BCC
n=1 SC
8*1/8=1 8*1/8+1=2

FCC
8*1/8+6*1/2=4
ATOMIC PACKING FACTOR OF SC

Crystal Structure
BODY CENTERED CUBIC STRUCTURE (BCC)
• Atoms touch each other along cube diagonals.
--Note: All atoms are identical; the center atom is shaded
differently only for ease of viewing.

ex: Cr, W, Fe (), Tantalum, Molybdenum

Crystal Structure
• Coordination # = 8

2 atoms/unit cell: 1 center + 8 corners x 1/8

 B-BODY CENTERED CUBIC (BCC)

 BCC has two lattice points so BCC Cr

y
is a non-primitive cell. st
al
St
 BCC has eight nearest neighbors. ru
ct
Each atom is in contact with its u
re

neighbors only along the body-

diagonal directions.
 Many metals (Fe,Li,Na..etc),
including the alkalis and several
b c
transition elements choose the
BCC structure.
a
 ATOMIC PACKING FACTOR: BCC
• APF for a body-centered cubic structure = 0.68

3a

2a
Close-packed directions:

R length = 4R = 3a
a
atoms
4 volume
unit cell 2  ( 3 a/4 ) 3
3 atom
APF =
volume
a3
unit cell
 FACE CENTERED CUBIC STRUCTURE (FCC)
• Atoms touch each other along face diagonals.
--Note: All atoms are identical; the face-centered atoms are shaded
differently only for ease of viewing.

Crystal Structure
ex: Al, Cu, Au, Pb, Ni, Pt, Ag
• Coordination # = 12

4 atoms/unit cell: 6 face x 1/2 + 8 corners x 1/8

Atomic Packing Factor of FCC

V atoms = 0,74

Crystal Structure
APF BCC
FCC
= 0.68
V unit cell

4 (0,353a)
ATOMIC PACKING FACTOR: FCC
• APF for a face-centered cubic structure = 0.74
maximum achievable APF
Close-packed directions:
length = 4R = 2a

2a
Unit cell contains:
6 x 1/2 + 8 x 1/8
a = 4 atoms/unit cell

atoms
4 volume
unit cell 4  ( 2 a/4 ) 3
3 atom
APF =
volume
a3
unit cell
 FCC Stacking
A
B Highlighting
the stacking
C

Crystal Structure
Highlighting the faces
 There are atoms at the corners of the unit cell and at the
center of each face.

Crystal Structure
 Face centered cubic has 4 atoms so its non primitive cell.
 Many of common metals (Cu,Ni,Pb..etc) crystallize in FCC
structure.
THE MOST IMPORTANT
CRYSTAL STRUCTURES

 Sodium Chloride Structure Na+Cl-

 Cesium Chloride Structure Cs+Cl-
 Hexagonal Closed-Packed Structure
 Diamond Structure
 Zinc Blende

Crystal Structure
 1 – SODIUM CHLORIDE STRUCTURE

Sodium chloride also

Crystal Structure

crystallizes in a cubic lattice,
but with a different unit cell.
 Sodium chloride structure
consists of equal numbers of
sodium and chlorine ions
placed at alternate points of a
simple cubic lattice.
 Each ion has six of the other
kind of ions as its nearest
neighbours.
 SODIUM CHLORIDE STRUCTURE

 If we take the NaCl unit cell and remove all the red Cl ions,

Crystal St
we are left with only the blue Na. If we compare this with the
fcc / ccp unit cell, it is clear that they are identical. Thus,
ru
ct
the Na is in a fcc sublattice. u
re
SODIUM CHLORIDE STRUCTURE
 This structure can be
considered as a face-centered-

Crystal Structure
cubic Bravais lattice with a
basis consisting of a sodium ion
at 0 and a chlorine ion at the
center of the conventional cell,

  
a / 2(x  y z )
 LiF,NaBr,KCl,LiI,etc
 The lattice constants are in the
order of 4-7 angstroms.
 2-CESIUM CHLORIDE STRUCTURE
CS+CL-

 Cesium chloride crystallizes in a

cubic lattice. The unit cell may be

Crystal Structure
depicted as shown. (Cs+ is teal,
Cl- is gold).

 Cesium chloride consists of equal

numbers of cesium and chlorine
ions, placed at the points of a
body-centered cubic lattice so
that each ion has eight of the
other kind as its nearest
neighbors.