Schematic cross section of a metal-oxide-

semiconductor field-effect transistor (MOSFET).

 Silicon Dioxide
SiO2 and the Si/SiO2 interface are the principal reasons for silicons
dominance in the IC industry.
SiO2:
Easily selectively etched using
lithography.
Masks most common impurities
(B, P, As, Sb).
Excellent insulator
( ).
High breakdown field
( 107 Vcm -1 )
Excellent junction passivation.
Stable bulk electrical properties.
Stable and reproducible interface
with Si.

No other known semiconductor/insulator combination has properties that approach

the Si/SiO2 interface.

2
Gate Oxide

3
 Thermal Oxidation
Oxidation is used in almost all stages of integrated curcuit production. Oxidation in a
controlled and reproducible way is extremely important.

Si surface can be oxidized by two techniques :

Dry Oxidation

Wet oxidation

Dry oxidation has better oxide quality

Oxidation involves a volume expansion

( 2.2X).
Especially in 2D and 3D structures, stress
effects play a dominant role.

4
 Birds Beak

Deposited Polysilicon

Locatio
no f Si N
3 4 Mask
Volume Original Si Surface
Expansion
SiO 2

Si Substrate

5
 SiO2
(b) Two-dimensional representation of a
quartz crystal lattice.
(a) Basic structural unit of silicon dioxide. Silicon-oxygen
bond is covalent.

Fused quartz and fused silica are types of

glass containing primarily silica in
amorphous (non-crystalline) form. Fused
silica is manufactured by melting naturally
occurring quartz crystals of high purity at
approximately 2000 C

(c) Two-dimensional representation of the

amorphous structure of silicon dioxide.
 Thermal Oxidation System

Oxidation systems are conceptually very simple.

Wafers are vertically located in the tube furnace

Pure O2 gas or water vapor is sent to the furnace from one end.

Wet oxidation is usually done by a technique called pyrogenic oxidation by forming the
water molecules in the furnace with O2 and H2 molecules

In practice today, vertical furnaces, RTO systems and fast ramp furnaces all find use.
 Basic model for the thermal oxidation of silicon.

Oxidation starts with the reaction of O2

or H2 molecules. A SiO2 film is formed
on the surface.

Oxidant molecules must travel through

the already grown oxide layer to reach
the interface for further oxidation.
 SiO2 Growth Kinetics Models
Deal and Grove Model
0.01 - 1 m 500 m
xO
The basic model for oxidation
CG was developed in 1965 by Deal
and Grove.
CS
CO

CI
C I
Gas Oxide Silicon

F1 F2 F3
CG is the bulk concentration of the gas in the furnace
Cs is the oxidant concentration adjacent to the oxide
surface.
Co is the oxidant concentration in the oxide at the outer
surface.
C* is the equilibrium concentration in the oxide.
CI is the oxidizing species concentration in the oxide
(Ficks diffusion law) adjacent to the SiO2/Si interface
 SiO2 Growth Kinetics Models
Under steady state conditions, F1 = F2 = F3 so
Limiting conditions

When the diffusivity is small ,

Ci = 0 and Co = C*.

This is called diffusion controlled case

When the diffusivity is large ,

Ci = Co = C* / (1+ ks/h) .

This is called reaction controlled case

Growth is related to the flux at the inteface

NI is the number of oxide

molecules incorporated into
a unit volume of oxide layer

10
 SiO2 Growth Kinetics Models
Integrating this equation, results in the linear parabolic model we find

where (parabolic rate constant) and (linear rate constant)

The oxide thickness can be written as a function of time :

where

Limiting Cases :

t >> t xo2 = B t (Parabolic law diffusion controlled regime)

( t + t ) << A2/4B xo = (B/A) ( t + t ) (Linear law reaction controlled regime)

 Rate constants
The rate constants B and B/A have physical meaning (diffusion controlled and (15)
interface reaction rate controlled case respectively).

Ambient B B/A

Dry O2 C1 = 7.72 x 102 2 hr-1 C2 = 6.23 x 106 hr-1 (16)

E1 = 1.23 eV E2 = 2.0 eV

Wet O2 .
C1 = 2.14 x 102 2 hr-1 C2 = 8.95 x 107 hr-1
E1 = 0.71 eV E2 = 2.05 eV
Numbers are for (111) silicon,
2 2 -1 8 -1
H2 O C1 = 3.86 x 10 hr C2 = 1.63 x 10 hr for (100) divide C2 by 1.68.
E1 = 0.78 eV E2 = 2.05 eV

T (C) E2 = 2.05 eV which is the enrgy

1200 1100 1000 900 800 required to break Si-Si bonds.
100

E1 = 0.71 eV which is the energy of

10
B/A H2O water diffusion
1
E1 = 1.23 eV which is the energy of
-1
B m 2 hr - 1

the O2 diffusion
B/A m hr

B H2O
0.1

B/A Dry O2
0.01
B Dry O2 Plots of B, B/A using the
0.001
values in the above Table.

0.0001
0.65 0.7 0.75 0.8 0.85 0.9 0.95 1
1000/T (Kelvin)
12
 Oxide thickness
0.7 2

0.6

1200C 1.5 1100 C

Oxide Thickness - microns

Oxide Thickness - microns

0.5
c)
0.4 1000 C
1100C
1
0.3
a) 900 C
1000C
0.2
0.5
b)
0.1
900C 800 C
800C 700 C
0 0
0 2 4 6 8 10 0 1 2 3 4 5 6 7 8 9 10
Time - hours
Time - hours
Calculated (100) silicon dry O2 Calculated (100) silicon H2O
oxidation rates using Deal Grove. oxidation rates using Deal Grove.

Example: a) 3 hrs in O2 @ 1100 C = 0.21 m + b) 2 hrs in

H2O @ 900 C = 0.4 m + c) 2 hrs in O2 @ 1200 C = 0.5 m total oxide
thickness.

13
 Dry vs. Wet Oxidation
Wet oxidation with water vapor has a higher parabolic rate constant and higher oxidation rate.
This is due to the higher solubility of (C*) of the water in the oxide layer.

C* (H2O) >> C* (O2) B(H2O) >> B(O2)

Wet oxidation is used to grow thick field oxides which are not so critical in device operation.
Important thin oxides (gate oxide of MOSFET) is grown by dry oxidation.
Water bubles can contaminate easily. To overcome this problem, pyrogenic oxidation is being
used. In this technique, O2 and H2 gases are sent to the furnace seperately. They react to form H2 O
before the oxidation
Oxidation and Orientation Dependence

Experimental results of silicon

dioxide thickness as a function of
reaction time and temperature for
two substrate orientations. (a)
Growth in dry oxygen.
(b) Growth in steam.

These curves are used to determine

the oxidation time in practical
applications.

The oxidation rate is dependent on

the substrate orientation. This is due
to the dependence of ks on the
surface atom concentration which
depends on the surface orientation.

B/A is orientation dependent

while
B is not.
Parabolic rate constant is a function
of diffusion through the oxide. It is
then not dependent on the surface
properties
 Dopant Dependence
Oxidation rate depends on the dopant concentration, especially at high doping level.
It is enhanced by dopants.

Incorporation of dopants into the oxide layer weakens the oxide structure, resulting
in a higher diffusion for the oxidizing species.

Another explanantion is the higher vacancy concentration in the higher doped layers,
that provides higher oxidation rates because oxidation is associated with the capture
of a Si atom by oxygen
 Dopant Redistribution during oxidation

A doping impurity will

resdistribute at the SiO2/Si
interface until its chemical
potential is same on each side of
the interface.

The ratio of the equilibrium

concentration of the impurity in Si
to that in SiO2 is called the
equilibrium segregation
coefficient.

m = CI (in Si) / CI (in SiO2)

a) Diffuison in oxide is slow (Boron ), b) Diffuison in oxide is fast (Boron-H2 ambieny),

c) Diffuison in oxide is slow (Phosphorous) d) Diffuison in oxide is fast (Gallium)
 Thin Oxide Growth Kinetics
A major problem with the Deal Grove model was recognized when it was first proposed - it does
not correctly model thin O2 growth kinetics.
Experimentally O2 oxides grow much faster for 20 nm than Deal Grove predicts.
MANY models have been suggested in the literature.
1. Reisman et. al. Model

(17)

Power law fits the data for all oxide thicknesses. a and b are experimentally extracted parameters.

2. Han and Helms Model

(18)

Second parallel reaction added - fits the data for all oxide thicknesses.
Second process may be outdiffusion of OV and reaction at the gas/SiO2 interface.

18
 Oxide Charges K+ Qm
SiO2 Na+
Four charges are associated with + Qot
insulators and insulator/semiconductor + - + -
interfaces. -
Qf - fixed oxide charge Transition + + + + + Qf
Qit - interface trapped charge Region x x x x x x
Qm - mobile oxide charge
Qot - oxide trapped charge Qit
Mobile ionic charges are mostly caused by ions like Silicon
Na+ and K+ that have very high diffusivity in oxide.
They are related to processing materials,
chemicals, ambient, handling.
Theri presence leads to treshold instabilites in the
MOSFETs Interface trapped charges is attributed to a
number af defects, lying at a very small
Cleaning of the wafers is extremely important distance of a few atomic layer from the
interface.
Fixed oxide charges are beleived to result from Unsaturated silicon bonds
non-perfect stoichiometry of the Si-O bonds in the Metallic impurities
transition region. These charges causes shift in the Metal Induced Gap states (MIGS)
treshold voltage of the MOSFETs Hydrogenation reduces their amount
significantly A low temperature anneal
An annealing in N2 ambient after the oxidation under hydrogen atmosphere is usually
reduces their amount significantly done after final metallization

Oxide trapped charges maybe positive or negative depending on the type of the carrier. It
can result from ionization radiation, or from hot carrier injection.