Chapter 2

Crystal structure, Miller indices and

Energy bands
 Classification of Solids
Solids can be classified according to the type of arrangement of atoms into
three main categories:
AMORPHOUS, POLYCRYSTALLINE, and CRYSTALLINE

AMORPHOUS STATE CRYSTALLINE STATE POLYCRYSTALLINE STATE

- AMORPHOUS solids are those in which atoms are placed randomly.

- CRYSTALLINE solids are those in which atoms are placed in a periodically ordered
structure. The atoms are ordered into a well-defined lattice that extends over very long
distances (crystalline in LRO).

- POLYCRYSTALLINE materials consist of small crystalline regions called grains,

separated by grain boundaries. The grains are of randomly different orientations
(crystalline in SRO).
 Crystal Lattice
- The periodic arrangement of atoms in a crystal is called a lattice.

- For a given semiconductor, there is a unit cell that is representative of the

entire lattice; by repeating the unit cell throughout the crystal, one can
generate the entire lattice.

-The Lattice constant (a) is the dimension of the unit cell in a certain direction.

Three-dimensional unit cell.

a=b=c, a=b=g=90°
 Basic crystal lattice types

Simple cubic (SC) Body-centered cubic (BCC) Face-centered cubic (FCC)

The number of atoms per unit cell for each of the above lattice types:

1- SC 8×(1/8) = 1 atoms/unit cell

2- BCC 8×(1/8) + 1 = 2 atoms/unit cell

3- FCC 8×(1/8) + 6×(1/2) = 4 atoms/unit cell

 Simple Cubic (SC)

a = 2R

Lattice Where:
R = atomic radius
a = lattice parameter

Hang 1 atom on each lattice

point

Crystal Structure

✓ Ex: Polonium (Z=84)

✓ Each atom has 6 nearest neighbours, therefore, coordination number is 6
 Body Centered Cubic (BCC)
Cubic Packing - BCC

a √3a

a
√2 a √2 a
a
√3a=4R
a=4R/√3
4R
a=
3
Where:
R = atomic radius ✓ Ex: Sodium
a = lattice parameter
✓ Coordination number for BCC structure is 8
 Face Centered Cubic (FCC)
Cubic Packing - FCC

4R=√2a

a=2R√2

a
√2 a

a
4R
a=
2
a = 2R 2
✓ Ex: Aluminum (Z=13) , Gold. (Z=79)
Where:
R = atomic radius ✓Coordination number for FCC structure is 12
a = lattice parameter
 Atomic Packing Factor
Fraction of solid sphere volume in a unit cell

APF = volume of atoms in unit cell

total cell volume

Example for FCC

✓ There are 4 spheres in the cell

✓ The volume of the spheres:

4R 4 3 16
4  R =  R 3
3 3
✓ What is the volume of the cube?
– a3 (length of side cubed)
✓ What is that in terms of R? (sphere radius)
– a = 2R√2
– (2R√2)3 = 16R3√2

volume of atoms in unit cell

(total sphere volume) Vs
APF = =
total cell volume Vc
16
 R3 
= 3 = = 0.74
3
16 R 2 3 2

The atomic packing factor for FCC is 0.74

(74% of the space is filled)
 Miller indices
Miller indices are group of numbers used to express different planes and
directions in the crystal lattice.

Planes

To represent a plane in the lattice using miller indices, follow the following
steps:

1. Find the intercepts of the plane with the axis relative to the lattice constant (a).
Call these intercepts x, y, z.

2. Find the inverse of the intercepts (1/x, 1/y, 1/z)

3. Use an appropriate multiplier to covert to whole numbers ➔ h k l.

4. Enclose the resulting numbers into curvilinear brackets (h k l).

Procedure to Find Plane Indices

Choose a plane that does not pass

through origin

Determine the x,y and z intercepts

of the plane

Find the reciprocals of the intercepts

YES Clear fractions by

Fractions?
multiplying by an integer
to determine smallest set
Place a ‘bar’ over the
of whole numbers
Negative indices

Enclose in curvilinear (hkl) where h,k,l

are miller indices of cubic crystal plane
for x,y and z axes. Eg: (111)
Notes
1- A plane that is parallel to an axis ➔ intercept = ∞
2- Parallel planes have the same miller indices
3- If the plane passes through the origin, choose another plane that is
parallel to it.
✓ Note that the Miller indices of a plane depend on both the plane and the
axes. Thus for the same plane (but diff. axes) the Miller indices could be
equivalent (Family of planes).

✓ Planes and their negatives are equivalent.

Family of planes {0 1 0}
Directions
To represent a direction in the lattice using miller indices, follow the
following steps:

1. Choose coordinates axes.

2. Choose a point on the direction that you know its coordinates.

3. Multiply by an appropriate multiplier to covert to whole numbers ➔u v w.

4. Enclose the resulting numbers into square brackets [uvw].

 Procedure to Find Direction Indices
Produce the direction vector till it
z
emerges from surface of cubic cell
(1,1/2,1) - (0,0,0)
(1,1/2,1)
Determine the coordinates of point = (1,1/2,1)
of emergence and origin y
(0,0,0) 2 x (1,1/2,1)
Subtract coordinates of point of x = (2,1,2)
Emergence by that of origin
The direction indices are [212]
NO
All are Convert them to
integers? smallest possible
YES integer by multiplying
Are any of the direction by an integer.
vectors negative?
NO
YES

Represent the indices in a square

Represent the indices in a square
bracket without comas with a
bracket without comas (Eg: [212] )
over negative index (Eg: [121])
3-17
 Notes

✓ Direction indices of a direction perpendicular to a crystal plane are

same as miller indices of the plane.
z

(110)
y
[110]
x
✓ The Miller indices of a direction depend on both the direction and the
axes. Thus for the same direction (but diff. axes) the Miller indices
could be equivalent (Family of directions).

[101] = [110]

< 110 >

 Example

Determine direction indices of the given vector.

Origin coordinates are (3/4 , 0 , 1/4). Emergence coordinates are (1/4, 1/2, 1/2).

Solution

✓ Subtracting origin coordinates from emergence coordinates,

(1/4, 1/2, 1/2) - (3/4 , 0 , 1/4) = (-1/2, 1/2, 1/4)

✓ Multiply by 4 to convert all fractions to integers

4 x (-1/2, 1/2, 1/4) = (-2, 2, 1). Therefore, the direction indices are [ 2 2 1 ]
 Diamond Structure
Silicon is referred to as a group IV element and has a diamond crystal
structure. Germanium is also a group IV element and has the same
diamond structure. A unit cell of the. Diamond structure is shown,

The tetrahedral Structure is

the basic building block of
the diamond lattice.
✓The top half again consists of two tetrahedral structures joined
diagonally, but which are at 90o with respect to the bottom half
diagonal.

✓An important characteristic of the diamond lattice is that any atom

within the diamond structure will have four nearest neighboring
atoms.
Diamond Structure Zencblende structure
Summary

Volume of atoms in unit cell

APF (Atomic Packing Factor ) = Volume of unit cell

Number of atoms in unit cell x

Atomic concentration nat = = 3
Volume of unit cell a

M at
x( )
Mass of all atoms per unit cell NA
Density = =
V olume of unit cell a3
M at is atomic mass , N A is A vogadro ' s Number
 Volume density = v =
Mass/Unit cell
Volume/Unit cell

Example:
Copper (FCC) has atomic mass of 63.54 g/mol and atomic radius of
0.1278 nm.

Solution:
4R 4  0.1278nm
a= = = 0.361 nm
2 2
Volume of unit cell = V= a3 = (0.361nm)3 = 4.7 x 10-29 m3
FCC unit cell has 4 atoms.
(4atoms )(63.54 g / mol )
Mass of unit cell = m = = 4.22 x 10-22 g
6.023 1023 atmos / mol

v m 4.22 10−22 g
= = = 8.98
g
V 4.7 10−29 m 3 cm 3
 Equivalent number of atoms whose
Planar atomic density =  p =
centers are intersected by selected area
Selected area

Example:
In Iron (BCC, a=0.287), The (110) plane intersects center of 5 atoms
(Four ¼ and 1 full atom).
Solution:
Equivalent number of atoms = (4 x ¼ ) + 1 = 2 atoms
Area of 110 plane = 2a  a = 2a 2
2
 =
2 (0.287)
p 2

17.2atoms 1.72  1013

= =
nm 2 mm 2
 Number of atomic diameters
intersected by selected length
Linear atomic density =  l =
of line in direction of interest
Selected length of line

Example:
For a FCC copper crystal (a=0.361), the [110] direction intersects 2
half diameters and 1 full diameter.

Therefore, it intersects ½ + ½ + 1 = 2 atomic diameters.

Length of line = 2  0.361nm

3.92atoms 3.92  106 atoms
l =
2atoms
= =
2  0.361nm nm mm

3-32
Wafer Fabrication
Polycrystalline
Furnaces
Czochralski process
Ingot
Slicing
Closer View
Of Polishing
Silicon Wafers

{100} n-type {100} p-type

{111} n-type {111} p-type

✓ Wafer Orientation has a strong effect on the MOSFET characteristics

Which orientation is preferred for MOSFET Fabrication!?

✓ Wafer Orientation has a strong effect on the deep etching process.

 Imperfections and Impurities in Solids
✓Up to this point, we have been considering an ideal single-crystal structure. In a
real crystal, the lattice is not perfect, but contains imperfections or defects; that is,
the perfect geometric periodicity is disrupted in some manner.

✓Imperfections tend to alter the electrical properties of a material and, in some

cases, electrical parameters can be dominated by these defects or impurities.

Defects have a profound impact on the macroscopic properties of

materials
 Types of Imperfections

✓ Vacancy atoms
✓ Interstitial atoms
Point defects
✓ Substitutional atoms 1-2 atoms (0-dimensional)

✓ Dislocations Line defects

1-dimensional

✓ Grain Boundaries Area defects

2-dimensional
 Point Defects
✓ Vacancies:
-vacant atomic sites in a structure.

Vacancy

distortion
of planes

✓ Self-Interstitials:
-"extra" atoms positioned between atomic sites.

self-interstitial

distortion
of planes
Point Defects: Impurities
 Linear defects
✓ Linear defects (Dislocations) are one-dimensional defects that cause
misalignment of nearby atoms.
✓ Linear defects are associated primarily with mechanical deformation.

Edge dislocation
extra half-plane of atoms
inserted in a crystal
structure; the edge of the
plane terminates within the
crystal.
Dislocation in a crystal is a line defect which is accompanied by lattice distortion and hence
a lattice strain around it
 Grain Boundaries

▪ regions between crystals

▪ transition from lattice of one region
to another

45
Report 1: Silicon- growth techniques?
1- Czochralski (CZ)
2- Float zone (FZ)
Energy bands
 Si : 1s 2 2s 2 2 p 6 3s 2 3 p 2

✓ Now we consider the atomic structure of Silicon which is known to contain

fourteen electrons that in turn occupy three different energy shells.

✓ Ten of the fourteen silicon atom electrons occupy deep-lying energy levels
close to the nucleus.

✓ The four remaining valence electrons are relatively weakly bound and are the
electrons involved in chemical reactions.

✓ We need only consider the n = 3 level for the valence electrons, since the first
two energy shells are completely full and are tightly bound to the nucleus. 48
✓The 3s contains two quantum states per atom. This state will contain two
electrons at T = 0 K.

✓The 3p contains six quantum states per atom. This state will contain the
remaining two electrons in the individual silicon atom.

✓As the interatomic distance decreases, the 3s and 3p states interact and
overlap. 49
✓At the equilibrium interatomic distance, the bands have splitted. But now
four quantum states per atom are in the lower band and four quantum state
per atom are in the upper band.

✓At absolute zero degrees, electrons are in the lowest energy state, so that
all states in the lower band (the valence band) will be full and all states in
the upper band (the conduction band) will be empty.

✓The band gap energy Eg between the top of the valence band and the
bottom of the conduction hand is the width of the forbidden energy band.

50
✓ The following plot shows the concept of allowed energy bands for the
particle propagating in the crystal lattice. Since the energy E has
discontinuities, we also have the concept of forbidden energies for the
particles in the crystal.

Third Band

Second Band

First Band

E-k diagram of free electron

E-k diagram or dispersion curve 51
 ✓ The E-K diagram can be described by:

E (k ) = A + ( −1) B cos( ka )

where = band number.

Gap
✓ The following figure shows the case in which
Band
the entire E versus k plot is contained within
- π /a <k < π /a. This plot is referred to as a
reduced k-space diagram, or a Reduced
Brillouin zones.

Reduced Brillouin zones

52
✓The material has an infinite number of allowed bands. However, most of the
bands simply have too high energy, and are usually disregarded.

✓Conversely, there are very low energy bands associated with the core orbitals.
These low-energy core bands are also usually disregarded since they remain
filled with electrons at all times, and are therefore inert.

✓The most important bands and band gaps are those with energies near the
Fermi level.

53
 Effective Mass
The movement of an electron in a lattice will, in general, be different from that of
an electron in free space.

Ftotal = Fext + Fint = ma

Fext = m *a

where the acceleration a is now directly related to the external force. The
parameter m* called the effective mass, takes into account the particle mass and
also takes into account the effect of the internal forces.

We can also relate the effective mass of an electron in a crystal to the E versus k
curves.

dE  2 k p 1 d 2E 1
= * = * 2 2
= *
dk m m  dk m

54
 E

If we consider an electron located in the first Fig. 1

Brillouin Zone shown in Fig. 1
-/a /a k

 Figure 2 depicts
d 2E dE2/dk2

dk 2 Fig. 2

-/a /a k

m*

 The electron effective mass is shown in Fig. 3

Fig. 3 -/a /a
2 k
d E
m* 2
/
dk 2

1 dE
 The individual electrons move with a velocity. v g (E ) =
dk

55
Example:
Consider an electron located in the first Brillouin Zone

E1 A1 B1 cos(ka )
Find m* and vg ?

Solution:

dE
= aB1 sin(ka )
dk
1 dE
v g =
dk
d 2E
2
= a 2
B 1 cos(ka )
dk
2 2
m = *
2 2
=
d E dk a 2 B 1 cos(ka )

56
 E
Notes

-/a /a k
o The effective mass m* is positive near the
m*
bottoms of all bands.

o The effective mass m* is negative near the -/a /a

tops of all bands k

o The radius of curvature of (b) is smaller (b)

than the radius of curvature of (a)
(a)
*
ma > mb *

k
57
Backup
 Bonding and Types of Solids
✓ When two atoms are brought together, the valence electrons interact with
each other and with the neighbor's positively charged nucleus. The result
of this interaction is often the formation of a bond between the two atoms,
producing a molecule.

✓ The formation of a bond means that the energy of the system of two
atoms together must be less than that of the two atoms separated.

✓ As the two atoms approach each other, the atoms exert attractive and
repulsive forces on each other.

FN = FA + FR
✓The potential energy V(r) of the two atoms can be found from,

dV ( r )
FN = −
dr
 V(r)
VR = Repulsive PE
V = Net PE

Vo

VA = Attractive PE

Curve (a)

✓ The variations of FA and FR with distance are different. Force FA varies slowly,
whereas FR varies strongly with separation and is strongest when the two
atoms are very close.
✓ In this state of equilibrium, the atoms are separated by a certain distance ro,
as shown in Figure. This distance is called the equilibrium separation and is
effectively the bond length. On the energy diagram, FN = 0 means dV/dr = 0.
Curve (b)
o r > ro
– the potential increases gradually, approaching 0 as r →∞
– the force is attractive
o r < ro
– the potential increases very rapidly, approaching ∞ at small
separation.
– the force is repulsive
The changes in interaction potential with distance can generally be
described quite well by the following expression:

V= decrease in potential energy+increase in potential energy

(due to attraction) (due to repulsion)

−a b
Or simply V (r ) = m + n
r r
V(r): The net potential energy of interaction as function of r
r : the distance between atoms, ions, or molecules
a,b: Proportionality constant of attraction and repulsion, respectively
m, n: The exponents m and n are characteristic of the type of binding and the
electronic structure.
For the bonding of ions m = 1 while for covalent bonding m = 6.
n varies for different electronic configurations.

Note : the binding occurs when m < n; otherwise repulsion dominates.