ELCT 705 :

Semiconductor Technology
Lecture 04: Crystal Growth and
Wafer Fabrication (CZ Crystal Growth)

Assoc. Prof. Dr. Mohamed Ragaa Balboul

Department of Electronic and Electrical Engineering

Types of Solids
The three general types of solids are

Amorphous

Order only within a few

atomic or molecular
dimensions.

Polycrystalline

High degree of order

over many atomic or
molecular dimensions.

Single-Crystal

High degree of order

throughout the entire
volume of the material.

Unit Cell

Unit cell is the smallest unit of volume that permits identical cells to be
stacked together to fill all space.
By repeating the pattern of the unit cell over and over in all directions,
the entire crystal lattice can be constructed.
CRYSTAL FACES

Atomic hard sphere model


a b

Unit Cell

and c

The vectors
define a unit cell, which can generate the entire lattice
by repeated translations. once the unit cell is defined, the rest of the structure
is defined as well.
Unit cell parameters (a, b, c, , , ) are chosen to best represent the highest
possible symmetry of the lattice.

Putting points
at corners

Lattice points

Lattice is an imaginary pattern

The 14 Bravais Lattices

Where Can I Put the Lattice Points? There is a limited number of possibilities !
The French scientist Auguste Bravais, demonstrated that only these 14 types of
unit cells are compatible with the orderly arrangements of atoms found in
crystals.

Name

# Bravais
lattice
1

a b c

90o

Monoclinic

abc

==90

Orthorombic
Hexagonal
Rhombohedral

4
1
1

abc

===90

a=bc

==90 =120

a=b=c

== 90

Tetragonal

a=bc

===90

Cubic

a = b= c

===90

Triclinic

Conditions

Cubic System

The three crystal structures which determine some of the basic

characteristics of these crystals.

Lattice constant

>90% of elemental metals crystallize upon solidification into 3 densely

packed crystal structures:

Simple Cubic

Body-Centered Cubic

Face-Centered Cubic

Atomic Packing Factor (APF)

APF = (volume of atoms in unit cell*/ volume of unit cell)

*assume hard spheres the volume of one atoms is (4/3) r3

Lattice constant

Unit cell contains: 8 x 1/8 =1 atom/unit cell

atoms
unit cell

atoms
volume

4
3
1 0.5a
3
APF
3
a volume

a 2R

unit cell

APF for a simple cubic structure = 0.52

maximum packing efficiency for equal-sized spheres

Atomic Packing Factor (APF)

Unit cell contains: (6 x )+ (8 x 1/8) = 4 atoms/unit cell

atoms
unit cell

4
4
3
APF

atoms
volume atoms

2a / 4
a3

a 4R / 2

volume

volume
unit cell

APF for a Face-centered cubic = 0.74

maximum packing efficiency for equal-sized spheres

Miller Indices
Miller indices : A shorthand notation to describe certain crystallographic
directions and planes in a material. Denoted by brackets. A negative
number is represented by a bar over the number.
[hkl] for the direction of a crystal such as [l00] for the x axis.
(hkl) for a plane that intercepts the x axis on the negative side of the origin.
{hkl}for planes of equivalent symmetry such as {l00} for (100), (010), and
(001) in cubic symmetry.
hkl for a full set of equivalent directions.

[111]
(111)

(100)

[100]

How to Get Miller Indices

1.

Find the intercepts x, y, z of the plane with the three basis axes
in terms of the lattice constant
2. Take reciprocals of these number and reduce to the smallest
three integers having the same ratio
3. Enclose the result in parentheses (hkl) as Miller indices.
Z

1.

Intercepts are 2, 1, 3
1 1 1
2. Reciprocals , ,
2 1 3
3. Clear the fractions (6)

3a

6 6 6
, ,
2 1 3

1a

4. Reduce to lowest term 3, 6, 2

2a

5. Millers are (362)

x

Inter-planner Spacing
The inter-planar spacing, d (normal distance
between two consecutive parallel planes) for a
cubic structure is given by

d( hkl )

a
h2 k 2 l 2

Silicon Crystal Structure

Silicon has a diamond cubic lattice structure.
This structure is most easily visualized as two
merged FCC lattices with the origin of the
second lattice offset from the first by a/4 in
all three directions.
Bulk properties in the silicon are generally
isotropic (independent of direction) because of
the cubic symmetry of the silicon crystal.
(111) Planes in silicon have the largest number
of silicon atoms per cm2 comparing with (100)
planes.
(111) Planes oxidize faster than (100) since the
oxidation rate is proportional to the number of
silicon atoms available for reaction.

Defects in Crystals

There are several types of defects such as point defects, line defects ,
area defects, and volume defects (depending on their dimensionality).
Point defects:
The first is simply a missing silicon lattice atom or
vacancy (V).
The second is an extra silicon atom (I)
1.

An atom sitting unbounded in one of the

available sites between silicon atom
(interstitial).

2. Two atoms sharing one lattice site, a defect

usually referred to as an interstitialcy.
In general, the concentrations of these defect
increases as temperature increases.

Dislocations

Defects in Crystals

One-dimensional defects in crystals are known

as dislocations.
The top part of the crystal contains an extra
plane of atom, which terminates at a
dislocation.
The dislocation itself is a linear defect in the
direction into the depth of the crystals.

Wafers are normally dislocation free, but

such defects can be generated during the
high temperature steps, particularly if thin
films present on the wafer surface generate
high stresses.
Dislocations are active defects in crystals,
that is they can move when subjected to
stresses.

Wafer Fabrication

Raw Materials and Purification

Quartz

Chemically quartzite is SiO2.

The first step is to convert the quartzite to
Metallurgical Grade Silicon or MGS; quartzite +
carbon source is heated to 2000 oC.
2C (solid) + SiO2 (solid)

Si(liquid) + 2CO (gas)

The MGS grade silicon is 98 % pure.

The second step is to convert the MGS to Electronic
Grade Silicon (EGS), usually by grinding the MGS to a
fine powder and then reacting it with gaseous HCl
(Hydrochloric acid) at elevated temperature; the
product is SiHCl compounds.
2SiHCl3 (gas) + 2H2 (gas)

2Si(solid) + 6HCl (gas)

This is accomplished in large CVD reactor. The EGS

is ultrapure polycrystalline silicon.

Czochralski (CZ) Crystal growth

Polysilicon Charge
Pieces of EGS are placed in silicon (SiO2) crucible with small amount of doped
silicon and melted.
The amount of dopant placed in the crucible with the silicon charge will determine
the doping concentration in the resulting crystal.

Ultra-Pure
Polysilicon Silica
+
Dopant

Silica Crucible
SiO2

Seed Dipping to the Melt

The melt temperature is stabilized at just above the silicon melting point (1417 oC).
A single-crystal seed is then lowered into the melt.
The crystal orientation of this seed will determine the orientation of the resulting
wafers.

Shoulder Growth
The seed is then slowly pulled out of the melt.
Silicon atoms from the melt bond to the atoms in the seed, lattice plane by lattice
plane, forming a single crystal as the seed is pulled upwards.

The diameter of the resulting crystal is controlled by the rate of pulling.

Start of Body Growth

During CZ crystal growth, the seed and the crucible are normally rotated in
opposite directions to promote mixing in the liquid and more uniform growth.
This also has the effect of increasing the corrosion of the crucible by melt; silicon
and oxygen being incorporated into melt.

Czochralski (CZ) Crystal Growth Methods

Seed
Single Silicon Crystal
Quartz Crucible

Water Cooled Chamber

Heat Shield
Carbon Heater
Graphite Crucible

Crucible Support
Spill Tray
Electrode

Czochralski (CZ) Crystal Growth Methods

Seed
Single Silicon Crystal
Quartz Crucible

Water Cooled Chamber

Heat Shield
Carbon Heater
Graphite Crucible

Crucible Support
Spill Tray
Electrode

Wafer Preparation and Specification

The process begins with shaping the grown crystal to uniform
diameter.
The crystal is normally grown slightly oversized and then trimmed
to the final diameter.
The next step is the actual sawing of the ingot into individual
wafer (Slicing).
This is usually accomplished with a rotating diamond-tipped blade
that cuts on its inside edge.
200 mm diameter wafers today are usually about 725 mm thick in
their final finished form.

The final step is to produce a mirror finish on one surface. A two

step process is used, chemical etching, followed by chemical
mechanical polishing.
The process removes the surface layers containing damage from
the various mechanical operations performed earlier.
This step producing a surface which is defect free and with mirror finish.

Czochralski (CZ) Crystal Growth

The relationship between the pull rate and the crystal diameter.
Freezing occurs between isotherms (constant temperature) X1 (liquid)
and X2 (Solid).
During the freezing process , heat is released to allow the silicon to
transform from the liquid to solid state (the heat of fusion).

Freezing zone

Heat Balance

This heat must be removed from the freezing interface, a process that
occurs primarily by heat conduction up the solid crystal .
Heat balance: latent heat of crystallization + heat conducted from melt to
crystal = heat conducted away. Thus we may write

dm
dT
dT
L
kL
A1 k S
A2
dt
dx1
dx2
L = Latent heat of fusion
KL = Thermal conductivity of liquid
KS= Thermal conductivity of solid
A1 and A2 are the cross-section areas.

dm
= Amount of silicon freezing per unit
dt time
dT
= Thermal gradient at isotherm x1
dx1
dT
= Thermal gradient at isotherm x2
dx2

The middle term, which will neglected, represents any additional heat that may
flow from the liquid to the solid because of the temperature gradients.

The Growth Rate of the Crystal

The rate at which the crystal (growth) is pulled out of the melt is simply:

dm
vP AN
dt

where vP is the pull rate of the crystal an N is the density of silicon. Thus,
the maximum pulling speed is

vPMAX

k S dT

LN dx2

In order to eliminate the temperature gradient term (dT) we need to

consider how the heat is conducted up the solid crystal and how it is
eliminated from the solid.
The latent heat of crystallization (A) is transferred from the liquid to the
solid, then transported away from the freezing interface primarily by
conduction up the solid crystal (B). The heat is last from the crystal by
radiation (C) and by convection. We will consider only radiation (more
simple).

Heat Losses due to Radiation

The Stefan-Boltzmann law describes heat loss due to radiation (C):

4

dQ (2rdx)(se T )

The 2rdx represents the radiating surface area, s is the S-B constant
and e is the emissivity of the silicon (temperature dependent).
The heat conducted up the crystal (B) is given by

dT
Q k s (r )
dx
2

where the r2 term is the cross sectional area of the crystal conducting
the heat and dT/dx is the temperature gradient.

Differentiating, we have
2

dQ
2 d T
2 dT dk s
2 d T
k S (r ) 2 (r )
k s (r ) 2
dx
dx
dx dx
dx

Heat Losses due to Radiation

Substituting in the S-B law (the differential equation describing the

temperature profile up the solid crystal

d 2T 2se 4

T 0
2
dx
kS r

The thermal conductivity of silicon Ks = kM (TM/T), where kM is the

thermal conductivity at the melting temperature TM, we find that

d 2T
2se
5

T
0
2
dx
kM rTM

This differential equation has a solution given by:

1/ 4

3k M rTM
T

8se

1
1/ 2

3k M rTM
x

2se

Maximum Crystal Pull Rate

After differentiation the last equation and evaluating x=0 and
substituting in the formula for vPMAX we have

vPMAX

LN

2se kM T
3r

5
M

The maximum crystal pull rate is inversely proportional to the square

root of the crystal radius.

Maximum Crystal Pull Rate

Example: Calculate the maximum pull rate of Silicon crystals for a 6

diameter CZ crystal.
2r = 6 = 15.24 cm

Latent heat of fusion L= 430 cal g-1

emissivity of the silicon = 0.55

Density of silicon N = 2.328 gm cm-3

melting temperature TM = 1690 K

thermal conductivity KM = 0.048 cal s-1cm-1K-1

S-B Constant = 5.67 x 10-5 erg cm-2s-1 K-4

1 erg = 2.39 x 10-8 cal

vPMAX

LN

2se kM TM5
3r

(430 cal

1
3
gm )(2.328 gm cm )

erg
cal
5
8 cal

2 5.67 10 5
0
.
55
0
.
048
1690
K
2
.
39

10
2
4

cm sec K
sec cm K
erg

37.62cm
1

0.00656 cm sec or 23.6 cm hr 1