UNIT I

CRYSTAL GROWTH, WAFER

PREPARATION, EPITAXY AND
OXIDATION
1


Advantages of Siover Ge

Sihas a larger bandgap(1.1 eVfor Siversus 0.66 eVfor Ge)
Sidevices can operate at a higher temperature (150oC vs100oC)
Intrinsic resistivityis higher (2.3 x 105-cm vs47 -cm)
SiO2is more stable than GeO2which is also water soluble
Siis less costly.
The processing characteristics and some material properties of silicon
wafers depend on its orientation.
The <111> planes have the highest density of atoms on the surface, so
crystals grow most easily on these planes and oxidation occurs at a higher
pace when compared to other crystal planes.
Traditionally, bipolar devices are fabricated in <111> oriented crystals
whereas <100> materials are preferred for MOS devices.

2
Defects
3

Any non-silicon atoms
incorporated into the
lattice at either a
substitutionalor
interstitial site are
considered point
defects


Point defects are important in the kinetics of diffusion and oxidation.
Moreover, to be electrically active, dopantsmust occupy substitutionalsites
in order to introduce an energy level in the bandgap.
4

Dislocations are line defects.
Dislocations in a lattice are dynamic
defects. That is, they can diffuse under
applied stress, dissociate into two or
more dislocations, or combine with
other dislocations.

Dislocations in devices are generally
undesirable, because they act as sinks
for metallic impurities and alter
diffusion profiles.
Electronic Grade Silicon

Electronic-grade silicon (EGS), a polycrystalline material of high purity, is the
starting material for the preparation of single crystal silicon. EGS is made from
metallurgical-grade silicon (MGS) which in turn is made from quartzite, which
is a relatively pure form of sand. MGS is purified by the following reaction:
Si(solid) + 3HCl (gas) SiHCl3 (gas) + H2 (gas) + heat
The boiling point of trichlorosilane(SiHCl3) is 32oC and can be readily
purified using fractional distillation. EGS is formed by reacting
trichlorosilanewith hydrogen:
2SiHCl3 (gas) + 2H2 (gas) 2Si (solid) + 6HCl (gas)

5


CzochralskiCrystal Growth


The Czochralski(CZ) process, which
accounts for 80% to 90% of worldwide
silicon consumption, consists of dipping a
small single-crystal seed into molten
silicon and slowly withdrawing the seed
while rotating it simultaneously.The
crucible is usually made of quartz or
graphite with a fused silica lining. After
the seed is dipped into the EGS melt, the
crystal is pulled at a rate that minimizes
defects and yields a constant ingot
diameter.

6
Oxygen in Silicon


Oxygen forms a thermal donor in silicon

Oxygen increases the mechanical strength of
silicon

Oxygen precipitates provide getteringsites for
unintentional impurities

7
Thermal Donors


Thermal donors are formed by the
polymerization of Siand O into complexes such
as SiO4in interstitial sites at 400oC to 500oC

Careful quenching of the crystal annihilates
these donors

8
Wafer Preparation
Gross crystalline imperfections are detected visually and defective crystals
are cut from the boule. More subtle defects such as dislocations can be
disclosed by preferential chemical etching
Chemical information can be acquired employing wet analytical techniques
or more sophisticated solid-state and surface analytical methods
Silicon, albeit brittle, is a hard material. The most suitable material for
shaping and cutting silicon is industrial-grade diamond. Conversion of
silicon ingots into polished wafers requires several machining, chemical,
and polishing operations

9

10

11

After grinding to fix the diameter, one or
more flats are grounded along the length of the
ingot. The largest flat, called the "major" or
"primary" flat, is usually relative to a specific
crystal orientation. The flat is located by x-ray
diffraction techniques.

The primary flat serves as a mechanical
locator in automated processing equipment to
position the wafer, and also serves to orient the
IC device relative to the crystal. Other smaller
flats are called "secondary" flats that serve to
identify the orientation and conductivity type of
the wafer.

The drawback of these flats is the reduction
of the usable area on the wafer. For some
200 mm and 300 mm diameter wafers, only a
small notch is cut from the wafer to enable
lithographic alignment but no dopanttype or
crystal orientation information is conveyed.

Slicing determines four wafer parameters:


Surface orientation (e.g., <111> or <100>)
Thickness (e.g., 0.5 0.7 mm, depending on
wafer diameter)
Taper, which is the wafer thickness variations
from one end to another
Bow, which is the surface curvature of the
wafer measured from the centerof the wafer
to its edge

12
13

Wafers
The wafer as cut varies enough in thickness to warrant an
additional lapping operation that is performed under pressure using
a mixture of Al2O3and glycerine.

Subsequent chemical etching removes any remaining damaged and
contaminated regions.Polishing is the final step. Its purpose is to
provide a smooth, specularsurface on which device features can be
photoengraved.

Typical Specifications for Silicon Wafers
14
Epitaxial Growth
Deposition of a layer on a
substrate which matches
the crystalline order of the
substrate
Homoepitaxy
Growth of a layer of the same
material as the substrate
Si on Si
Heteroepitaxy
Growth of a layer of a
different material than the
substrate
GaAs on Si
Ordered,
crystalline
growth; NOT
epitaxial
Epitaxial
growth:
General Epitaxial Deposition
Requirements
Surface preparation
Clean surface needed
Defects of surface duplicated in epitaxial layer
Hydrogen passivation of surface with water/HF
Surface mobility
High temperature required heated substrate
Epitaxial temperature exists, above which deposition is ordered
Species need to be able to move into correct crystallographic
location
Relatively slow growth rates result
Ex. ~0.4 to 4 nm/min., SiGe on Si
General Scheme
Thermodynamics
Specific thermodynamics varies by process
Chemical potentials
Driving force
High temperature process is mass transport controlled, not very sensitive
to temperature changes
Steady state
Close enough to equilibrium that chemical forces that drive growth are
minimized to avoid creation of defects and allow for correct ordering
Sufficient energy and time for adsorbed species to reach their lowest
energy state, duplicating the crystal lattice structure
Thermodynamic calculations allow the determination of solid composition
based on growth temperature and source composition
Kinetics
Growth rate controlled by kinetic
considerations
Mass transport of reactants to surface
Reactions in liquid or gas
Reactions at surface
Physical processes on surface
Nature and motion of step growth
Controlling factor in ordering
Specific reactions depend greatly on method
employed
Kinetics Example
Atoms can bond to flat surface, steps,
or kinks.
On surface requires some critical radius
Easier at steps
Easiest at kinks
As-rich GaAs surface
As only forms two bonds to underlying
Ga
Very high energy
Reconstructs by forming As dimers
Lowers energy
Causes kinks and steps on surface
Results in motion of steps on surface
If start with flat surface, create step
once first group has bonded
Growth continues in same way
Vapor Phase Epitaxy
Specific form of chemical vapor deposition (CVD)
Reactants introduced as gases
Material to be deposited bound to ligands
Ligands dissociate, allowing desired chemistry to reach
surface
Some desorption, but most adsorbed atoms find proper
crystallographic position
Example: Deposition of silicon
SiCl
4
introduced with hydrogen
Forms silicon and HCl gas
Alternatively, SiHCl
3
, SiH
2
Cl
2
SiH
4
breaks via thermal decomposition
Precursors for VPE
Must be sufficiently volatile to allow
acceptable growth rates
Heating to desired T must result in pyrolysis
Less hazardous chemicals preferable
Arsine highly toxic; use t-butyl arsine instead
VPE techniques distinguished by precursors
used
Varieties of VPE
Chloride VPE
Chlorides of group III and V elements
Hydride VPE
Chlorides of group III element
Group III hydrides desirable, but too unstable
Hydrides of group V element
Organometallic VPE
Organometallic group III compound
Hydride or organometallic of group V element
Not quite that simple
Combinations of ligands in order to optimize
deposition or improve compound stability
Ex. trimethylaminealane gives less carbon
contamination than trimethylalluminum
Other Methods
Liquid Phase Epitaxy
Reactants are dissolved in a
molten solvent at high
temperature
Substrate dipped into
solution while the
temperature is held constant
Example: SiGe on Si
Bismuth used as solvent
Temperature held at 800C
High quality layer
Fast, inexpensive
Not ideal for large area layers
or abrupt interfaces
Thermodynamic driving force
relatively very low
Molecular Beam Epitaxy
Very promising technique
Elemental vapor phase
method
Beams created by
evaporating solid source in
UHV
Molecular Beam Epitaxy
Source: William R. Wiley Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, Richland, WA
25
Molecular Beam Epitaxy: Idea !
Objective: To deposit single crystal thin films !

Inventors: J.R. Arthur and Alfred Y. Chuo (Bell Labs, 1960)

Very/Ultra high vacuum (10
-8
Pa)

Important aspect: slow deposition rate (1 micron/hour)

Slow deposition rates require proportionally better vacuum.
26
Molecular Beam Epitaxy: Process
Ultra-pure elements are heated in separate quasi-
knudson effusion cells (e.g., Ga and As) until they
begin to slowly sublimate.

Gaseous elements then condense on the wafer,
where they may react with each other (e.g., GaAs).

The term beam means the evaporated atoms do
not interact with each other or with other vacuum
chamber gases until they reach the wafer.




27
Molecular Beam
A collection of gas molecules moving in the same direction.

Simplest way to generate: Effusion cell or Knudsen cell


Test Chamber
Sample
Orifice
Oven
Pump
Knudson cell effusion beam system
28
Molecular beam
Oven contains the material to make the beam.

Oven is connected to a vacuum system through a
hole.

The substrate is located with a line-of-sight to the
oven aperture.

From kinetic theory, the flow through the aperture is
simply the molecular impingement rate on the
area of the orifice.
29
Molecular Beam
Impingement rate is:


The total flux through the hole will thus be:



The spatial distribution of molecules from the orifice of a
knudsen cell is normally a cosine distribution:






|
.
|

\
|
|
.
|

\
|
= =
m
kT
kT
p
v n I
t
8
4
1
4
1
mkT
r p
IA Q
t
t
2
2
= =
|
.
|

\
|
=
t
0 cos
4
1
' v n I
30
Molecular Beam
The intensity drops off as the square of the distance from the
orifice.






High velocity, greater probability; the appropriate distribution:









0
t
t
0
cos
2
,
1 cos
2
2
|
.
|

\
|
(

=
|
.
|

\
|
|
.
|

\
|
=
L
r
mkT
p
I
or
L
IA I
sub
sub
m kT where
dv
v v
n
dn
v
/ 2
exp 2
2
2
4
3
=
|
|
.
|

\
|

|
|
.
|

\
|
=
o
o o

31
Molecular Beam
Integrating the equation gives:


as the mean translational energy of the
molecules



kT E
tr
2 =

I

# Intensity is maximum in the
direction normal to the orifice and
decreases with increasing , which
causes problems.

# Use collimator, a barrier with a
small hole; it intercepts all of the
flow except for that traveling towards the sample.
32
MBE: In-situ process diagnostics
RHEED (Reflection High Energy Electron Diffraction) is used to monitor the
growth of the crystal layers.

Computer controlled shutters of each furnace allows precise control of the
thickness of each layer, down to a single layer of atoms.

Intricate structures of layers of different materials can be fabricated this way
e.g., semiconductor lasers, LEDs.

Systems requiring substrates to be cooled: Cryopumps and Cryopanels are used
using liquid nitrogen.
33
ATG Instability
Ataro-Tiller-Grinfeld (ATG) Instability: Often encountered during MBE.

If there is a lattice mismatch between the substrate and the growing film, elastic energy is accumulated in the growing film.

At some critical film thickness, the film may break/crack to lower the free energy of the film.

The critical film thickness depends on the Youngs moduli, mismatch size, and surface tensions.


34
Principle uses of Si dioxide (SiO
2
) layer in Si
wafer devices
Surface passivation
Doping barrier
Surface dielectric
Device dielectric
OXIDATION

What is oxidation?
Formation of oxide layer on wafer
High temperature
O
2
environment
Doping barrier
In doping need to create holes in a surface
layer in which specific dopants are introduced
into the exposed wafer surface through diffusion
or ion implantation
SiO
2
on Si wafer block the dopants from reaching
Si surface
All dopants have slower rate of movement in SiO
2

compared to Si
Relatively thin layer of SiO
2
is required to block the
dopants from reaching SiO
2


Cont..
SiO
2
possesses a similar thermal expansion
coefficient with Si
At high temperature oxidation process, diffusion
doping etc, wafer expands and contracts when it is
heated and cooled
close thermal expansion coefficient, wafer does not
warp
Si
Dopants
SiO
2
layer as dopant barrier
Surface dielectric
SiO
2
is a dielectric does not conduct electricity
under normal circumstances
SiO
2
layer prevents shorting of metal layer to
underlying metal
Oxide layer
MUST BE continuous; no holes or voids
Thick enough to prevent induction
If too thin SiO
2
layer, electrical charge in metal layer cause a
build-up charge in the wafer surface cause shorting!!
Thick enough oxide layer to avoid induction called field
oxide
Wafer
Oxide layer
Metal layer
Dielectric use of SiO
2
layer
S D
Field oxide
MOS gate
source Drain
Types of oxidation
1. Thermal oxidation
2. High pressure oxidation
3. Anodic oxidation
Device oxide thicknesses

Most applications of semiconductor are
dependent on their oxide thicknesses
Silicon dioxide
thickness,
Applications
60-100 Tunneling gates
150-500 Gates oxides, capacitor
dielectrics
200-500 LOCOS pad oxide
2000-5000 Masking oxides, surface
passivation
3000-10000 Field oxides
Thermal oxidation mechanisms
Chemical reaction of thermal oxide growth
Si (solid) + O
2
(gas) SiO
2
(solid)
A
Oxidation temperature 900-1200C
Oxidation: Si wafer placed in a heated
chamber exposed to oxygen gas
SiO
2
growth stages
Si wafer
Si wafer
Si wafer
Initial
Linear
Parabolic
Oxygen atoms combine readily with Si atoms
Linear- oxide grows in equal amounts for each time
Around 500 thick
In a furnace with O
2
gas environment
Above 500, in order for oxide layer to keep growing, oxygen
and Si atoms must be in contact
SiO
2
layer separate the oxygen in the chamber from the wafer
surface
Si must migrate through the grown oxide layer to the
oxygen in the vapor
oxygen must migrate to the wafer surface
Three dimension view of SiO
2
growth by thermal
oxidation
Si substrate
SiO
2

SiO
2
surface
Original SiO
2
surface

Linear oxidation


Parabolic oxidation of silicon

where X = oxide thickness, B = parabolic rate constant, B/A = linear rate
constant, t = oxidation time
Parabolic relationship of SiO
2
growth parameters


where R = SiO
2
growth rate, X = oxide thickness, t = oxidation time


t
A
B
X =
Bt X =
2
t
X
R =
Cont..
Implication of parabolic relationship:
Thicker oxides need longer time to grow than thinner
oxides
2000, 1200C in dry O
2
= 6 minutes
4000, 1200C in dry O
2
= 220 minutes (36 times longer)
Long oxidation time required:
Dry O
2

Low temperature

Dependence of silicon oxidation rate constants on
temperature
Kinetics of growth

Si is oxidised by oxygen or steam at high temperature
according to the following chemical reactions:
Si (solid) + O
2
(gas) SiO
2
(solid) (dry oxidation)
Or
Si (solid) + 2H
2
O (gas) SiO
2
(solid) + 2H
2
(gas) (wet oxidation)
Also called steam oxidation, wet oxidation, pyrogenic steam
Faster oxidation OH
-
hydroxyl ions diffuses faster in oxide layer
than dry oxygen
2H
2
on the right side of the equation shows H
2
are trapped in
SiO
2
layer
Layer less dense than oxide layer in dry oxidation
Can be eliminated by heat treatment in an inert
atmosphere e.g. N
2


2 mechanisms influence the growth rate of the oxide
1. Actual chemical reaction rate between Si and O
2

2. Diffusion rate of the oxidising species through an already grown oxide
layer
No or little oxide on Si the oxidising agent easily reach the Si surface
Factor that determine the growth rate is kinetics of the silicon-oxide
chemical reaction
Si is already covered by a sufficiently thick layer of oxide
Oxidation process is mass-transport limited
Diffusion rate of O
2
and H
2
O through the oxide limit the growth rate is
diffusion of O
2
and H
2
O through the oxide
A steam ambient is preferred for the growth of thick oxides:H
2
O
molecules smaller than O
2
thus, easier diffuse through SiO
2
that cause
high oxidation rates
Si oxidation

Mass transport of O
2
molecules from gas ambient towards the
Si through a layer of already grown oxide
Flux of O
2
molecules is proportional to the differential in O
2

concentration between the ambient (C
*
) and oxide surface (C
0
)

Where h is the mass transport coefficient for O
2
in the gas phase
Diffusion of O
2
through the oxide is proportional to the
difference of oxygen concentration between the oxide surface
and the Si/SiO
2
interface. The flux of oxygen through the oxide,
F
2
becomes


Where,
C
i
= oxygen concentration at theSi/SiO
2
interface
D = diffusion coefficient of O
2
or H
2
O in oxide
t
ox
= oxide thickness


2 . 5 ......... ..........
0
2
ox
i
t
C C
D F

=
1 . 5 ..... )......... (
0
*
1
C C h F =

Kinetics of the chemical reaction between
silicon and oxygen is characterised by reaction
constant, k:

In steady state, all flux terms are equal: F
1
= F
2

= F
3
. Eliminating C
0
from the flux equations,
we can obtain:


4 . 5 ......... ..........
1
*
D
t k
h
k
C
C
ox s s
i
+ +
=
3 . 5 ....... ..........
3 i s
C k F =
If N
0x
is a constant representing the
number of oxidising gas molecules
necessary to grow a unit thickness of
oxide, one can write:


The solution to this differential equation
is:


5 . 5 .......
1
*
D
t k
h
k
C k N
C k N F N
dt
dt
ox s s
s ox
i s ox ox
ox
+ +
= = =
6 . 5 ..........
1
0 0
* } }
=
+ + t
ox
t
s ox
ox s s
dt dt
C k N
D
t k
h
k
ox
If t
ox
=0 when t=0, th eintegration yields:



Or



Defining new constant A and B in terms of D, k
s
, N
ox
and C
*
:





We can obtain:

From which we find t
ox
:
7 . 5 ........ 0
2
*
2
=
|
|
.
|

\
|
+ + dt C N t
h
D
k
D t
ox ox
s
ox
8 . 5 .. .......... 2
1 1
2
* 2
t C DN t
h k
D t
ox ox
s
ox
=
|
|
.
|

\
|
+ +
10 . 5 ...... .......... 2
9 . 5 .. ..........
1 1
2
*
ox
s
N DC B
and
h k
D A
=
|
|
.
|

\
|
+ =
11 . 5 . .......... ..........
2
Bt At t
ox
= +
12 . 5 ....... ..........
4 /
) (
1
2
1 2
|
|
.
|

\
|
+
+ =

B A
t A
t
ox
t
t is introduced to take into account the possible presence of an oxide layer on
the Si before thermal oxide growth being carry out
Oxide layer can be a native oxide layer due to oxidation of bare Si by ambient air
or thermally grown oxide produced during a prior oxidation step
t=0 if the thickness of the initial oxide is equal to zero
When thin oxides are formed the growth rate is limited by the kinetics of
chemical reaction between Si and O
2
.
Eq. 5.12 becomes:


Which is linear with time.
The ratio is called linear growth coefficient, and is dependent on crystal
orientation of Si

( ) 13 . 5 . .......... t + = t
A
B
t
ox
A
B
When thick oxides are formed, the growth rate is limited by the diffusion rate of
oxygen through the oxide. Eq 5.12 becomes:


The coefficient B is called parabolic growth coefficient and is independent on
crystal orientation of Si.
The parabolic growth coefficient can be increased:
Increase the pressure of the ambient oxygen up to 10-20 atm (high pressure
oxidation)
The linear growth coefficient can be increased:
Si consists of high concentration of impurities e.g. phosphorous: increase point
defects in the crystal which increase the oxidation reaction rate at the Si/SiO
2
interface
Oxidation process also generate point defects in Si which enhance diffusion of
dopants. Some dopants diffuse faster when annealed in oxidising ambient than in
neutral gas such at N
2


14 . 5 .... .......... ) ( Bt t B t
ox
~ + = t
Oxidation rate
Controlled by:
1. Wafer orientation
2. Wafer dopant
3. Impurities
4. Oxidation of polysilicon layers
1. Wafer orientation
Large no of atoms allows faster oxide growth
<111> plane have more Si atoms than <100> plane
Faster oxide growth in <111> Si
More obvious in linear growth stage and at low
temperature
2. Wafer dopant(s) distribution
Oxidised Si surface always has dopants; N-type or
P-type
Dopant may also present on the Si surface from
diffusion or ion implantation
Oxidation growth rate is influenced by dopant
element used and their concentration e.g.
Phosphorus-doped oxide: less dense and etch faster
Higher doped region oxidise faster than lesser doped
region e.g. high P doping can oxidise 2-5 times the
undoped oxidation region
Doping induced oxidation effects are more obvious in
the linear stage oxidation


Schematic illustration of dopant distribution as a function of position is the SiO
2
/Si structure indicating
the redistribution and segregation of dopants during silicon thermal oxidation
Distribution of dopant atoms in Si after
oxidation is completed
During thermal oxidation, oxide layer grows down
into Si wafer- behavior depends on conductivity
type of dopant
N-type: higher solubility in Si than SiO
2
, move down to
wafer. Interface consists of high concentration N-type
doping
P-type: opposite effect occurs e.g Boron doping in Si
move to SiO
2
surface causes B pile up in SiO
2
layer and
depletion in Si wafer change electrical properties

3. Oxide impurities
Certain impurities may influence oxidation
rate
e.g. chlorine from HCl from oxidation
atmosphere increase growth rate 1-5%
4. Oxidation of polysilicon
Oxidation of polysilicon is essential for
polysilicon conductors and gates in MOS
devices and circuits
Oxidation of polysilicon is dependent on
Polisilicon deposition method
Deposition temperature
Deposition pressure
The type and concentration of doping
Grain structure of polysilicon

Thermal oxidation method
Thermal oxidation energy is supplied by heating a
wafer
SiO
2
layer are grown:
Atmospheric pressure oxidation oxidation without
intentional pressure control (auto-generated pressure);
also called atmospheric technique
High pressure oxidation high pressure is applied
during oxidation
2 atmospheric techniques
1.Tube furnace
2.Rapid thermal system

Oxidation methods
Thermal oxidation
Atmospheric
pressure
Tube furnace Dry oxygen
Wet oxygen

Rapid thermal Dry oxygen
High pressure Tube furnace Dry or wet
oxygen
Chemical oxidation
Anodic
oxidation

Electrolytic cell Chemical