Diamond Cubic Unit Cell

DIAMOND CUBIC AND GRAPHITE STRUCTURES OF
CARBON
Introduction:
 Polymorphism in a material is the ability of a
solid material to have more than one crystal
structure decided by thermodynamic
parameters.
 Polymorphism can be found in any crystalline
material including polymers, minerals, and
metals.
 If the change in structure is reversible then the
polymorphism is known as ‘allotropy’.
 Allotropy is a behavior exhibited by certain
chemical elements. These elements can exist
in two or more different forms, known as
allotropes of that element.
 In each allotrope, the atoms of an element
are bonded together differently.
 The allotropes of carbon are diamond and
graphite.
 Learning objectives:
 To understand the diamond cubic structure
and the graphite structure.
Diamond cubic unit cell
 Normally, there are 8 corner atoms and 6 face-
centered atoms in an FCC unit cell.
 One tetrahedral void is present at a distance of
one-fourth of the body diagonal from each
corner in the FCC unit cell.
 Thus 8 tetrahedral voids are present along the
four body diagonals in the FCC unit cell.
 In a diamond cubic unit cell, 4 out of 8
tetrahedral voids are occupied by carbon
atoms in addition to 8 corner carbon atoms
and, 6 face-centered carbon atoms during the
formation as shown in Fig.1.35b.
Mathematical model of a diamond cubic unit cell
According to the mathematical modeling, a

diamond cubic unit cell is formed due to the
interpenetration of two FCC unit cells through one
of the body diagonals.
 Let O and O′ be the origin of the first and
second FCC unit cells. The coordinates of the
point are (0, 0, 0). The point O′ indicates the
position of a tetrahedral void.
 We consider that the carbon atom at O′
approaches the carbon atom at O along the
body diagonal. The length of the body diagonal
is . The interpenetration is stopped at a
distance of one-fourth of the body-diagonal
when the carbon atom at the origin O′
of the second unit cell touches the carbon atom

at the origin O of the first unit cell.
On resolving the vector along the axes X, Y,
and Z, we get
This is valid owing to the following reasons. .

This shows that the coordinates of the
tetrahedral void at O′ are
The coordinates of the other 3 tetrahedral voids

are
 Each carbon atom occupying the tetrahedral
void in the unit cell is covalently bonded to
one carbon atom at its nearest corner and
the three carbon atoms at its nearest face
centres.
 This means the coordination of the carbon
atom in the diamond cubic cell is 4.
 Thus four tetrahedrons are present inside the
diamond cubic unit cell.
 The angle between two adjacent covalent
bonds in the tetrahedron is 109.5º and the
length of each bond is 0.153 nm.
Contribution from the 8 corner atoms = 1
Contribution from the 6 face-centered atoms = 3
Contribution from the 4 atoms that occupied four
tetrahedral voids = 4
Therefore, the number of atoms effectively
present in a diamond cubic unit cell = 8.
 This shows that 34% volume of the diamond
cubic unit cell alone is occupied by atoms and
the remaining 66% of its space is void. The
elements such as silicon, germanium, and α-tin
have a diamond cubic structure. As the atomic
packing factor of a diamond cubic unit cell is
low, it is called a loosely packed structure.
Projection of atoms
 There are 5 layers of carbon atoms in the
diamond cubic unit cell.
 The projection of the atoms located in the
second layer, third layer, and fourth layer on the
bottom layer indicates their heights at
appropriate positions marked on the bottom
layer of the diamond cubic unit cell.
 C1, C2, C3, and C4 are the four corners of the
bottom face. The heights of the atoms at these
corners are zero. Also, the height of the bottom
face-center atom (F5) is zero.
 Four tetrahedral voids TV1, TV2, TV3, and TV4
are occupied by carbon atoms.
 The height of the atom occupying the
tetrahedral void TV1 is
tetrahedral void TV2 is also
 The voids TV1 and TV2 are located above the
points on the face diagonal ‘C1C3’ at a
distance of from C1 to C3 respectively.
tetrahedral void TV3 is . The height of
the atom occupying the tetrahedral void TV4
is also
 The position of the voids TV3 and TV4 are above
the points on the face diagonal ‘C2C4’ at a
distance of from C2 to C4 respectively.
 The face-centered atoms F1, F2, F3, and F4 are
positioned at the same height of above
the midpoints of the sides ‘C1C2’, ‘C2C3’, ‘C3C4’,
and ‘C4C1’respectively.
Properties of the diamond crystal
 The density of the diamond is 3500 kg/m3.
 The diamond crystal is extremely hard and
transparent.
 It is a poor electrical conductor but an excellent
thermal conductor.
 In the graphite structure, a carbon atom has a
strong covalent bond with three other carbon
atoms in its plane at an angle of 120º involving
an sp2 hybrid orbital and a weaker Van der
Walls bond with a fourth atom lying in the
adjacent layer.
 All atoms in a single layer are linked to give flat
hexagons.
 The C-C covalent bond length is 0.142 nm and
the height between the two adjacent layers is
0.34 nm.
Properties of graphite structure
 The density of graphite is 2100 kg/m3.
 Graphite is a soft, black, flaky, slippery solid,
and a moderate electrical conductor.
 Graphite is used as a lubricant and in pencils
since its layers cleave readily.
Calculation of the density of a material using the
lattice constants
 In this mathematical model, the crystal
structure of a given material must be known.
 The mass of a unit cell is owing to the mass of
atoms effectively present in the volume of the
unit cell.
S.No. Parameters SC BCC FCC HCP
1 Atomic radius
2 Nearest neighbor distance a a

3 Coordination number 6 8 12 12
4 No. of atoms per unit cell 1 2 4 6
5 Volume occupied by atoms
6 Volume of the unit cell
7 Atomic Packing Factor 0.52 0.68 0.74 0.74

Diamond Cubic Unit Cell

Uploaded by

Copyright:

Available Formats

Diamond Cubic Unit Cell

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Diamond Cubic Unit Cell

Uploaded by

Copyright:

Available Formats

DIAMOND CUBIC AND GRAPHITE STRUCTURES OF

According to the mathematical modeling, a

of the second unit cell touches the carbon atom

This is valid owing to the following reasons. .

The coordinates of the other 3 tetrahedral voids

2 Nearest neighbor distance a a

5 Volume occupied by atoms

6 Volume of the unit cell

7 Atomic Packing Factor 0.52 0.68 0.74 0.74

You might also like