Department of Electrical and

Electronics Engineering

BITS Pilani Dr. Satyendra Kumar Mourya,

Pilani Campus
Assistant Professor
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Common steps of device fabrication technology

 Wafer Growth
 Wafer Cleaning
 Oxidation
 Epitaxy
 Diffusion
 Ion implantation
 Lithography
 Etching
 Metallization
 Packaging

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 Bridgman method

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 Czochralski method

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 Oxidation

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 Properties of thermally grown SiO2
• It is amorphous. • Atomic density: 2.31022 molecules/cm3
• Stable, reproducible and conformal SiO2 growth (For Si, it is 51022 atoms/cm3)
• Refractive index: n=1.46
• Melting point: 1700C
• Dielectric constant: =3.9 (why not =n2?)
• Density: 2.21 g/cm3 (almost the same as Si that
• Excellent electrical insulator: resistivity  > 1020
is 2.33 g/cm3) cm, energy gap Eg=8-9 eV.
• Crystalline SiO2 [Quartz] = 2.65gm/cm3ti • High breakdown electric field: >107 V/cm

Conformal
growth

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 The Si/SiO2 interface

Thermal oxide
(amorphous)

Si substrate
(single crystal)

The perfect interface between Si and SiO2 is one major reason

why Si is used for semiconductor devices (instead of Ge…)
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 Application of SiO2 in IC industry

STI

STI: shallow trench isolation

Very good etching selectivity between Si and SiO2 using HF

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 Diffusion mask for common dopants
SiO2 can provide a selective mask against
diffusion at high temperatures. (DSiO2 << Dsi)
Oxides used for masking are 0.5-1μm thick.

(not good for Ga)

Can also be used for Mask thickness (m)

mask against ion
implantation

Diffusion time (hr)

SiO2 masks for B and P 10
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 Use of oxide in MOSFET

Gate oxide, only 0.8nm thick!

As insulation material between interconnection

levels and adjacent devices

LOCOS: local oxidation isolation; STI: shallow trench isolation 11

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 Oxide Structure

Amorphous tetrahedral network

Basic structure of silica: a silicon atom

tetrahedrally bonds to four oxygen atoms

The structure of silicon-silicon dioxide interface:

some silicon atoms have dangling bonds. 12
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 Oxide Structure

Single crystal (quartz)

2.65 g/cm3

Amouphous (thermal
oxide). 2.21 g/cm3

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 Thermal silicon oxidation methods

A three-tube horizontal
furnace with multi-zone
temperature control

Vertical furnace
Wet oxidation using H2 and O2 is more (not popular)
popular (cleaner) than using H2O vapor.

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 Thermal oxidation equipment

• The tubular reactor made of quartz or glass, heated by resistance.

• Oxygen or water vapor flows through the reactor and past the
silicon wafers, with a typical velocity of order 1cm/s. 15
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 Thermal oxidation in practice
1. Clean the wafers (RCA clean, very important)
2. Put wafers in the boat
3. Load the wafers in the furnace
4. Ramp up the furnace to process temperature in N2 (prevents oxidation from occurring)
5. Stabilize
6. Process (wet or dry oxidation)
7. Anneal in N2. Again, nitrogen stops oxidation process.
8. Ramp down

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 Surface profilometry (Dektak): mechanical
thickness measurement
Oxide etched away by HF over part
of the wafer and a mechanical stylus
is dragged over the resulting step.
Stylus
Mirror image of stylus

stylus

AFM can also be used for thickness measurement.

(AFM: atomic force microscopy) 18
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Thickness determination by looking the color
Relative illumination intensity

Film thickness (nm)

• Oxide thickness for constructive interference (viewed from above =0o) Xo=k/2n, n=1.46,
k=1, 2, 3…
• Our eye can tell the color difference between two films having 10nm thickness difference. 20
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Optical thickness measurement: Ellipsometry
Very accurate (1nm accuracy)
Quarter
Light wave plate
source Filter Polarizer Analyzer Detector

Film being
measured
Substrate

• After quarter wave plate, the linear polarized light becomes circular polarized, which is
incident on the oxide covered wafer.
• The polarization of the reflected light, which depends on the thickness and refractive
index (usually known) of the oxide layer, is determined and used to calculate the oxide
thickness.
• Multiple wavelengths/incident angles can be used to measure thickness/refractive index
of each film in a multi-film stack.
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 Electrical thickness measurement: C-V of MOSFET

Small AC voltage is
applied on top of the DC
voltage for capacitance
measurement.

Substrate is N-type. Electron is majority

carrier, hole is minority carrier.
a. Accumulation: positive gate voltage
attracts electrons to the interface.
b. Depletion: negative gate bias pushes
electrons away from interface. No
charge at interface. Two capacitance in
series.
c. Inversion: further increase (negative)
gate voltage causes holes to appear at
the interface. 22
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 At/after inversion: P-type substrate here
For low frequency, (minority) charge generation at the (previous slide N-type)
interface can follow the AC field to balance the charge
at the gate, so Cinv=Cox.
For high frequency, the gate charge has to be balanced
by the carrier deep below the interface, so Cinv-1 = Cox-
1 + C -1.
Si

Deep depletion: for high scanning speed (the DC

voltage scan fast into large positive voltage), depletion
depth Xd must increase to balance the gate charge.

Parameter from C-V measurement:

• Dielectric constant of Si & SiO2
• Capacitor area
• Oxide thickness
• Impurity profile in Si
• Threshold voltage of MOS capacitor

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 The Use
• Masks
• Surface Passivation
To protect the junctions  Only those
portions are exposed  metal contacts.
• Gate oxide
• Isolation between devices
Different requirements

Mask Gate oxide

Thick oxide Thin oxide

Little worry about More Concern about

the quality the quality

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 Cont..

• It has to be a chemical reaction between silicon and oxygen

• In CVD, it can be done by Oxidation
• Substrate is reacting with the gas that is oxygen or steam or some oxygen containing
species and forming silicon dioxide.

• Si+O2  SiO2

Si
Si

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 Cont..

• Silicon is being consumed in order to form the silicon dioxide.

Q. How much it is below and how much above?

Si + O2 SiO2
28 32 60

• 60 grams of silicon dioxide will be formed by consuming 28 grams of silicon

Volume * Density

A x tox x ρSiO2  WSiO2 A x tSi x ρSi  WSic

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 Cont..

• One expression for the silicon thickness that is consumed

• One expression for the oxide thickness that is grown
tSi 28 A 2.27
  = 0.45
tox A 2.33 60

• if 1000 A0 of silicon dioxide is grown  consumed 450 A0 of silicon

SiO2 550A0
450A0

Si

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Numerical Problem 1

Q3. An optimized wet oxidation process was used to grow the SiO2 layer on a p-type (100)
silicon substrate for a certain amount of time in a 250 nm technology node. If in this process,
1.44×1017 number of silicon atoms are consumed. Calculate the thickness of the SiO2 layer
grown on the top of the Si wafer, provided that the surface area of the wafer is 1 cm2.
(ρSi=2.33 g/cm3, Atomic mass of silicon= 28, Avogadro’s number (NA) =6.023×1023)

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Solution

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 Cont..

Methods

Chemical Anodic Thermal

Methods oxidation oxidation

Boil silicon in Electrolytic bath VLSI Technology

nitric acid (HNO3)

Quality is the best

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 Thermal Oxidation Si
silicon sample

Oxide growth
put inside furnace
Left of the
Raise furnace temperature interface
Si

allow either oxygen or

water vapour to flow
oxidizing
species move in
silicon will react either with oxygen or
with water to form silicon dioxide.

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 Cont..
Si + O2 = SiO2 Dry
Si + 2H2O = SiO2 + 2H2 Wet
Oxygen species or oxidant Either oxygen or water vapour

Note: during thermal

oxidation process

the oxidizing species

move inside

The interface will not be move through the oxide

affected by contamination layer and reacts with the
silicon at this interface.
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 Kinetics of oxidation

Deal and Grove model: Journal of Applied Physics,AIP

GAS SiO2 Si

CG C*=Equilibrium
concentration of oxidising
CS Co
species in oxide
Ci

F1 F2 F3

CG = concentration of oxidising species in gas

CS = concentration of oxidising species next to gas oxide interface
Co = concentration of oxidising species at outer oxide surface
Ci = concentration of oxidising species at the inner oxide surface
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 Cont..

F1 = Flux of the oxidising species in the bulk of the gas

From the bulk of the gas right next to the oxide gas interface

F1 α CG - CS
F1 = hG (CG –CS)

Proportionality constant / gas phase mass transfer coefficient

Gas law: PV = kT

F1 
hG
PG  PS  (1)
kT
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 Cont..

Henry’s Law: in equilibrium the concentration of a species within a solid

is proportional to the partial pressure of that species in the surrounding
gas.

C*  HPG H = Henry’s constant

Co  HPS
Rewrite equation (1)

h G  C* Co
F1 
HkT
F1  h C  Co 
*
(2)

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 Cont..

F2 is related to the movement of the oxidizing species through the

existing oxide layer.
Co  Ci  Concentration gradient
F2  D (3)
x Existing oxide thickness

F3 is related to the reaction of silicon with the oxidizing species

availability of the oxidizing species at the

oxide silicon interface
F3  KSCi (4)

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 Cont..

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 Cont..

Case 2: D∞ x/D very small

The concentration of oxidizing species is
same from the outer surface to the inner
Co≈C* SiO2 Ci
surface

reaction limited

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 Growth rate
Si + O2 = SiO2 Dry
Si + 2H2O = SiO2 + 2H2 Wet

• one molecule of silicon reacts with one molecule of oxygen to give

one molecule of silicon dioxide
• one molecule of silicon is going to react with two molecules of water
to give one molecule of silicon dioxide

N1 = no. of oxidant molecules per unit vol. of oxide

For O2 = 2.27 x 1022

For H2O = 2 x 2.27 x 1022

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 Cont..

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 Cont..

Case I: t  ∞
x  Bt Parabolic growth

for any oxidation process  two rate constants associated with this.

Linear rate constant

Parabolic rate constant

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 Oxidation rate constants

Temp (0C) Type A (μm) B (μm2/hr) B/A (μm/hr)

920 Wet 0.5 0.203 0.406
Dry 0.235 0.005 0.021
1200 Wet 0.05 0.72 14.4
Dry 0.04 0.045 1.12

C* = 5.2 x 1016 (Dry)

= 3.0 x 1019 (Wet)
2DC*
B N1 is larger for wet oxidation
N1
to grow one molecule of silicon dioxide
we needed two molecules of water
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 Cont..

Case I: T=9200C, B/A  linear rate constant

Wet Dry

0.406 0.021
20 times less

B  parabolic rate constant

Wet Dry

0.203 0.005
40 times less

Case II: Similar comparisons for T=12000C

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 Cont..
Wet oxidation  faster growth rate
Why?
2DC*
B N1 is larger for wet oxidation
N1

to grow one molecule of silicon dioxide

we needed two molecules of water

N1 large  B small

But the equilibrium concentration (C*) of the oxidizing species for wet
oxidation (5x1019)  three order higher than dry oxidation (5.2x1016)

B is much higher  wet oxidation

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 Cont..
Grow thicker oxide  grow it using steam ambient
Compare the same for different temperatures

9200 12000
0.203 0.72
D
 EA
 
D  D0 exp  
 kT 
Dry  1.24 eV
EA  Activation Energy Experimental Data
Wet  0.7 eV

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 Cont..
B/A

9200 12000

0.406 14.4
KS

Reaction rate  temperature

A

9200 12000 A  2D 1  1 

 KS h 

0.5 0.05
D in the numerator & KS in the denominator
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 Cont..

• Both of them will exhibit the famous linear parabolic relationship.

• Wet oxidation  much thicker oxide
• Growth rate is higher for higher temperature.
• The experimental curve of dry oxidation is not passing through the origin
• Some xi at t=0
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 Cont..
• Only problem  when you grow thin oxide through dry oxide

• Fails to predict
Explanations

Initially, the oxide growth rate is much

faster than predicted by Deal & Grove
x

~270A0

time

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 Cont..
• (1 1 1) oriented crystal  higher rate of oxide growth than  the (1 0 0) oriented
crystal

• (1 1 1) oxidized faster  more number of atoms per unit area

• In the linear region  oxidation depends on reaction rate Widely

spaced
• In the parabolic region  oxidation depends on diffusion Closely
spaced
Q. Whether oxidation rate depends on doping?
• heavily doped with boron (p+)  oxidizes faster  Diffusion of oxidising species
is faster
• heavily doped with phosphorous (n+)  Reaction rate of oxidising species is faster
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Numerical Problem 4
Typical oxidation rate constants are appended below in the table for a temperature-dependent dry and wet oxidation
process. In order to oxidize the silicon wafer oxidation was carried out in the following sequence dry/wet/dry at 920,
1000, and 1200 ºC respectively. The time of oxidation for the dry and wet processes was 120 and 40 minutes,
respectively. Assume native oxide thickness to be zero. Calculate the following.

(a) The final oxide thickness is grown on the top of the silicon wafer.
(b) The position of SiO2/Si interface w.r.t initial Si surface, if the initial thickness of Si wafer was 300 μm.

Temp. Type A (μm) B (μm2/hr) B/A (μm/hr)

920 ºC Wet 0.5 0.203 0.406

Dry 0.235 0.0049 0.0208

1000 ºC Wet 0.226 0.287 1.27

Dry 0.165 0.0117 0.071

1200 ºC Wet 0.05 0.720 14.40

Dry 0.040 0.045 1.12

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Solution

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 Dopant Redistribution
• silicon is doped either p-type or n-type, moderately or heavily  carry
out the oxidation  Q. what happens to the impurity?
equilibrium concentration of dopant in silicon
Segregation coefficient K=
equilibrium concentration of the dopant in SiO2

• Either K<1 or >1

• another factor  how fast the dopant can diffuse through oxide?

• Mask  SiO2 blocks the movement of dopants  Diffuse

slowly through the oxide

• Exception: Ga  diffuse very fast  not preferred as p-type doping

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 Cont..

Two facts to concern

Segregation coefficient Dopant diffuses fast or slow

(a) (b) (c) (d)

K<1 K<1 K>1 K>1
Slow Fast Slow Fast
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 Cont..

equilibrium concentration is more in

• Case I: K < 1 SiO2 than in Si
• Eg: ‘B’  slow diffuser through SiO2  preferably go into SiO2
1. Si side  B concentration is less than on the SiO2 side
2. Si-SiO2 interface  there is a depletion of B

1. B profile inside the SiO2  concentration high

(K<1)
2. Stay constant  slow diffuser  then it falls

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 Cont..

• Case II: K < 1 & Fast diffuser

• A practical example  boron in a hydrogen ambient.
then boron can diffuse fast through silicon dioxide.
• normal boron diffusion is never done in hydrogen
ambient, but always in oxygen or nitrogen ambient

• Case III: K > 1 & Slow diffuser

• Eg  ‘P’  reason for common n-type dopant

• Pile-up of phosphorous in Si side

• SiO2 side  same story as of Case I

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 Cont..
• Case IV: K > 1 & Fast diffuser
• Eg  Ga
• Point instead of pile-up, it falling in Si side -interface

Ga is an extremely fast diffuser.

There is no chance for gallium to pile up

at the interface, it just diffuses out.

forced out through the oxide. just falls

drastically

draws the gallium out from

this interface region

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 Cont..

• Oxide thickness problems  heavily p-type and a heavily n-type silicon

• Eg.1: Si with heavily Phosphorous doped (n+)

Case III  pile-up

• thermal oxidation  inwards.
• heavily phosphorus piled up region  getting oxidized
• This affects the reaction rate.
• modifying the quality of this region.
• the oxidation process is governed by the reaction rate
• you can expect a thicker oxide growth.

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 Cont..

• Eg.2: Si with heavily Boron doped (p+)

Case I

• Boron has preferentially come inside the oxide.

• increased presence of boron in SiO2  affect the diffusion of the
oxidizing species through the oxide.
• aid in the diffusion of the oxidizing species  silicon dioxide, which
is heavily boron doped.
• silicon wafer  faster oxide growth rate

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 Practical Aspects of thermal oxidation

• To avoid contamination  the furnaces, the tubes  made of quartz

Two options

Pass pure oxygen Pass steam

Suppose requirement is to grow thick oxide.

increase the temperature increase the time of oxidation

Range 900-12000C Amorphous SiO2  desired

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 Cont..
• High temperature  thermal stress  &  amorphous oxide can get
devitrified • > 1μm
• The process of crystallization

• Instead of amorphous  poor quality crystalline SiO2  neither good for masking nor
useful for isolation

• Challenge: How to grow good quality thicker oxide?

A  2D 1  1 
*
B 2DC
PG C* Both B & B/A
 KS h  N1

B C* Oxidation under high pressure

 • C*αPG
A  1  1
N1  
 KS h 
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 Cont..

• Three parameters to play: temperature, time, and pressure

• By increasing the P  afford to cut down either the T or the time

• Thermal stress, budget, cost, electricity

Quality of oxide

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 Cont..
• SiO2  ideally insulator  should be no charges

• Charges  non-idealities
1. Interface trapped Charges  mechanical damage / broken bonds

• Takes part in the

electronic activity

• Available energy states

2. Fixed Oxide Charges  incomplete oxidation

Thermal oxidation  inward  interface oxidized at last 

chance of incomplete, SiOx  x<2  positive in nature

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 Cont..
2. Fixed Oxide Charges  unavoidable  can’t be discharged  +ve 
push the threshold voltage towards -ve

[Link] Trapped Charges  causes  HCE (Avalanche injection) & radiation

environment  e-h pairs (holes may get trapped)

4. Mobile Ionic Charges  sodium & potassium  +ve

Can be checked through

proper CV analysis

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 Cont..
Q. How to minimize these charges? Move towards metal

1. Mobile ions: Free to move

Move towards Si-

Important to reduce
SiO2 interface
this contamination

• to remove/fix this mobile ionic impurity  chlorine oxidation

can available in many forms :

Trichloroethyl
Chlorine gas, Cl 2 Anhydrous hydrogen ene, TCE
chloride, HCl

hazardous material C2HCl3, liquid

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 Cont..

Q. How does it help in fixing the mobile ions?

Ans: mobile ions: Na+ or K+  sodium chloride and potassiumchloride

Fix the ions: no longer free to move

Cleanliness of the lab/system
No detrimental effect on electrical
performance

• Some more points on chlorine oxidation:

• Reduce oxidation induced stacking faults (OISF)

• Lifetime of the device
Broken Si bonds  interface to bulk
• Note: small quantity (less than 1015 cm-2) of Chlorine is beneficial
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 Cont..
Q. Oxide trapped charges? After processing / device fabrication
Exception: ion beam etching

Problem: Spread all over the forbidden energy gap

Affect the electronic activity &

device performance

• Mostly due to dangling bonds

• Solution: post oxidation annealing in hydrogen at comparatively lower

temperature (4500C).
• Reacts with Si & satisfies the dangling bonds

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 Cont..
Q. Fixed oxide charges? SiOx (incomplete oxidation) +ve

Recall the fabrication of

Hamper the Vth
enhancement nMOS
oxidation  at a very high
temperature, 12000C

the sample temperature is being

lowered

still oxidizing ambient is being

maintained.
Deal Triangle
Fixed oxide charges (1012 cm-2)
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 Cont..

• Q. What can be done to stop this incomplete oxidation process?

• At the end of the oxidation process

1. close the oxygen gas flow and create an inert ambient

(nitrogen or argon) & reduce the T.

2. It will stop the oxidation (no incomplete oxidation)

• At the end of the oxidation process  before taking out the samples  nitrogen
flushing for 15/20 minutes  to remove the traces of oxygen before the temperature is
lowered  fixed oxide charges < 1010 cm-2

• Home work: Anodic Oxidation

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 BITS Pilani
Pilani Campus

Thank You

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