A Presentation on

“Growth kinetics for thermal oxidation of silicon, the

special case for VLSI/MEMS technology”

By
Prachi Sharama
Dept. of ECE, Banasthali University, Banasthali.

Compiled by:-

1. Kulwant Singh
2. Soney Varghese
3. Uvais V N
4. Prachi Sharama
5. Ashish Kumar

12/08/2021 1
 Overview

Thermally Grown Oxides Deposited Oxides

Oxide
Thickness

1 µm Field Oxides Backend Insulators

Between Metal Layers

0.1 µm Masking Oxides

Masking Oxides

Pad Oxides
10 nm
Gate Oxides
Tunneling Oxides

1 nm Chemical Oxides from Cleaning

Native Oxides

Thickness & uses of SiO2 in Si Technology

• SiO2 and the Si/SiO2 interface are the principal reasons for silicon’s dominance
in the IC industry.
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 Advantages/ applications SiO2:-

• Easily selectively etched using

lithography.
• Masks most common impurities
(B, P, As, Sb).
• Excellent insulator
(   10 cm,). Eg  9 eV
16

• 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.

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 Future Projection Si Technology
Year of Production 1998 2000 2002 2004 2007 2010 2013 2016 2018

Technology Node (half pitch) 250nm 180nm 130nm 90 nm 65 nm 45 nm 32 nm 22 nm 18 nm

MPU PrintedGate Length 100nm 70 nm 53 nm 35 nm 25 nm 18 nm 13 nm 10 nm

DRAM Bits/Chip (Sampling) 256M 512M 1G 4G 16G 32G 64G 128G 128G

MPU Transistors/Chip (x106) 550 1100 2200 4400 8800 14,000

GateOxide Tox Equivalent (nm) 1.2 0.9 0.7 0.6 0.5 0.5
MPU
GateOxide Tox Equivalent (nm) 1.5 1.2 0.9 0.8 0.7 0.7
Low Operating Power
GateDielectric Leakage 170 230 330 1000 1670 1670
(nA/µm @ 100ÞC) MPU
ThicknessControl (% 3 ) < ±4 < ±4 < ±4 < ±4 < ±4 < ±4
Min Supply Voltage (volts) 1.8-2.5 1.5-1.8 1.2-1.5 0.9-1.2 0.8-1.1 0.7-1-0 06-0.9 0.5-0.8 0.5-0.7

Adapted from “NTRS”SIA, 1997

12/08/2021 5
 Manufacturing Methods & Equipment

• Oxidation systems are conceptually

very simple.
Quartz
Tube • In practice today, vertical furnaces,
Wafers
RTO systems and fast ramp furnaces
all find use.
Quartz Carrier

Resistance Heating Si  O2  SiO2

O2 H2
Si  2H 2 O  SiO2  2H 2
Conceptual Silicon Oxidation System



• Thermal oxidation potentially being used in many places in chip
fabrication. In practice, deposited SiO2 layers are increasingly being used in
case of back-end process.
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 Charge Associated with the SiO2/Si System

• Four charges are associated with

K+ Qm insulators and
SiO2 Na+ insulator/semiconductor
+ Qot
+ - + - interfaces.
- • Qf - fixed oxide charge
Transition + + + + + Qf • Qit - interface trapped charge
Region x x x x x x
• Qm - mobile oxide charge
Qit • Qot - oxide trapped charge
Silicon

12/08/2021 7
 Measurement Methods
• Physical measurement
– Scanning tunneling microscope(STM)
– Atomic Force microscope (AFM)
– SEM etc..
• Optical Measurement
– Color chart by Pliskin and Conrad
• Electrical measurement- The CMOS Capacitor

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 A. Planar growth kinetics

0.01 - 1 µm ­500 µm
xO

CG
• The basic model for oxidation
was developed in 1960 by Deal
CS
and Grove.
CO
Si  O2  SiO2 (1)
CI
C
I
Gas Oxide Silicon Si  2H 2 O  SiO2  2H 2 (2)

F1 F2 F3


F1  hG C G  C S  (3)

N C O  C I 
F2  D  D  (4)
x  x O 

F3  k SC I (5)
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
 • Under steady state conditions, F1 = F2 = F3 so
C* C*
CI   (6)
k k x k x
1 S  S O 1 S O
h D D
 k x 
C * 1  S O 
  D 
CO   C* (7)
k k x
1 S  S O
h D
• Note that the simplifications are made by neglecting F1 which is a very good
approximation.

• Combining (6) and (7), we have
dx F k SC *
 
dt N 1  k S k S x O  (8)
N 1 1   
 h D 

• Integrating this equation, results in the linear parabolic model.


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 x 2O  x 2i x O  x i
 t (9)
B B/ A
2DC *
whereB  (parabolic rate constant) (10)
N1
B  C* C *k S
and   (linear rate constant) (11)
A  1 1  N1
N 1   
 k S h 

• (9) can also be written with oxide thickness as a function of time.


A  t  (12)
x O   1  2  1
2  A / 4B 

x 2i  Ax i
where  (13)
B



12/08/2021 11
• The rate constants B and B/A have physical meaning (oxidant diffusion and
interface reaction rate respectively).
Ambient B B/A
B  C 1 expE1 / kT (14)

Dry O2 C1 = 7.72 x 102 µ2 hr-1 C2 = 6.23 x 106 µ hr-1

E1 = 1.23 eV E2 = 2.0 eV B
 C 2 expE2 / kT
Wet O2 .

C1 = 2.14 x 102 µ2 hr-1 C2 = 8.95 x 107 µ hr-1 A (15)

E1 = 0.71 eV E2 = 2.05 eV

H2O C1 = 3.86 x 102 µ2 hr-1 C2 = 1.63 x 108 µ hr-1 • Numbers are for (111) silicon,
E1 = 0.78 eV E2 = 2.05 eV
for (100) divide C2 by 1.68.

T (ÞC)
1200 1100 1000 900 800
100

10
B/A H2O

1 • Plots of B, B/A using the

1
-
B µm hr 1
-

B/A µm hr

B H2O values in the above Table.

2

0.1
B/A Dry O2
0.01
B Dry O2

0.001

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

Oxide Thickness - microns

0.6

1200ÞC 1.5 1100 ÞC

0.5

0.4 1000 ÞC
1100ÞC
1
0.3
900 ÞC
1000ÞC
0.2
0.5

0.1
900ÞC 800 ÞC
800ÞC 700 ÞC
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.

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 B. 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
 1 
b

 x i b 
x O  at  t i 
b
or x O  at     (16)
  a  
 
• Power law “fits the data” for all oxide thicknesses.
• a and b are experimentally extracted parameters.
• Physically - interface reaction controlled, volume expansion and viscous flow

of SiO2 control growth.
2. Han and Helms Model
dx O B1 B2
  (17)
dt 2x O  A1 2x O  A2
• Second parallel reaction added - “fits the data” ” for all oxide thicknesses.
• Three parameters (one of the A values is 0).

12/08/2021 14
 3. Massoud et. al. Model
dx O B  x 
  C exp O  (18)
dt 2x O  A  L 
• Second term added to Deal Grove model - higher dx/dt during initial growth.
• L ≈ 7 nm, second term disappears for thicker oxides.
 along with the DG model, \ used in process simulators.
• Easy to implement .

• Data agrees with the Reisman, Han and Massoud models. (800˚C dry O2 model
comparison below.)
0.03

0.025

Deal Grove Model ( = 8 hrs)

0.02
Oxide Thickness - microns

Reisman et. al. Model

0.015

Han & Helms Model

0.01

Deal Grove Model ( = 0)

0.005

0
0 2 4 6 8 10
Time - hours

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 C. 2D SiO2 Growth Kinetics

1
1

1
1 1.3 1.2

1 1 1.3 1 1

Si substrate Si substrate
1.3

Deposited Polysilicon
• Oxidation involves a volume
expansion
(≈ 2.2X).
• Especially in 2D and 3D Volume Original Si Surface
structures, stress Expansion
effects play a dominant role. SiO 2

Si Substrate

12/08/2021 16
 Etched Si Ring
a)
• These effects were investigated in
detail experimentally by Kao et. al.
Si Substrate
about 15 years ago.
• Typical experimental results below.
Side Views Top Views

b)

Polysilicon
c)

SiO2

Si

d)

(Kao et.al)
12/08/2021 17
 • Several physical mechanisms seem to be
1.1
important:
1200 ÞC • Crystal orientation
1.0
• 2D oxidant diffusion
1100 ÞC
0.9 • Stress due to volume expansion
• To model the stress effects, Kao et. al.
Normalized Oxide Thickness

0.8
1000 ÞC suggested modifying the Deal Grove
0.7
.
parameters.
1100 ÞC
0.6 900 ÞC
  V    V 
0.5 1000 ÞC 800 ÞC k S (stress)  k S exp n R exp t T  (19)
900 ÞC  kT   kT 
0.4
 PVD 
0.3 Convex Radii
D(stress)  Dexp  (20)
Concave Radii  kT 
0.2 
0.1  PVS 
1 µm 0.2 µm 0.125 µm C (stress)  C exp
* *
 (21)
 kT 
2 3 5 
where  n and  t are the normal and
0 1 4 6 7 8
1/r µm-1
(Kao et.al)
tangential stresses at the interface.
VR, VT and VS are reaction volumes and

 are fitting
 parameters.
12/08/2021 18
•In addition, the flow properties of the SiO2 need to be described by a stress
dependent viscosity  S VC / 2kT
(stress)  (T) (22)
sinh S VC / 2kT

Where  S is the shear stress in the oxide and VC is again a fitting parameter.
.

-0.4

Parameter Value -0.2
Si 3 N 4
 VR 0.0125 nm3
SiO 2

0
VD 0.0065 nm3
VS, VT 0 0.2 Silicon

Microns
3
VC 0.3 nm @ 850˚C
0.4
0.72 nm3 @ 1050˚C
(T) - SiO2 3.13 x 1010 exp(2.19 eV/kT) poise 0.6

(T) - Si3N4 4.77 x 1010 exp(1.12 eV/kT) poise

0.8

-0.8 -0.4 0 0.4 0.8 -0.8 -0.4 0 0.4 0.8

Microns Microns

• These models have been implemented in modern process simulators and allow
them to predict shapes and stress levels for VLSI structures (above right).
• ATHENA simulation: Left - no stress dependent parameters, Right - including
stress dependence.

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 D. Point Defect Based Models
• The oxidation models we have considered to this point are macroscopic models
(diffusion coefficients, chemical reactions etc.).

• There is also an atomistic picture of

O2 Diffusion
* V oxidation that has emerged in recent
years.
• Most of these ideas are driven by the
H2O
volume expansion occurring during
I * I oxidation and the need for
“free volume”.
Oxide Silicon

• In Chapter 3 we described internal oxidation in the following way:

1  2 SiSi  2OI  2V  SiO2  2I  stress (23)

• Surface oxidation can be thought of in the same way.



12/08/2021 20
 • The connection between oxidation and other processes can then be modeled as
.

shown below.
O2

Si 3 N 4
Surface 0 SiO 2
Recombination
G R Inert Diffusion
OED

Microns
0.5
I
Bulk Recombination *
Inert 1.0
Diffusion Buried Dopant Marker Layer OED

1.5
-2 -1 0 1 2
Microns

Example - ATHENA simulation of

OED.
• Oxidation injects interstitials to create “free volume” for the oxidation process.
• Oxidation can also consume vacancies for the same reason.
• These processes increase I concentrations and decrease V concentrations in
nearby silicon regions.
• Any process (diffusion etc) which occurs via I and V will be affected.

12/08/2021 21
 E. Complete Process Simulation of Oxidation
• Many of these models (and others in Chapter 6), have been implemented in
programs like SUPREM.

• Simulation of an advanced
0
isolation structure (the SWAMI
process originally developed by
Microns

0.4
.

Hewlett-Packard), using
SSUPREM IV. The structure
prior to oxidation is on the top
0.8
left. A 450 min H2O oxidation at
1000 ˚C is then performed which
results in the structure on the
0
top right. An experimental
structure fabricated with a
Microns

0.4 similar process flow is shown

on the bottom right. The stress
0.8 levels in the growing SiO2 are
shown at the end of the
-1 0 1
Microns oxidation on the bottom left.

12/08/2021 22
 Summary of Key Ideas

• Thermal oxidation has been a key element of silicon technology since its
inception.

• Thermally, chemically, mechanically and electrically stable SiO2 layers on silicon

distinguish silicon from other possible semiconductors.

• The basic growth kinetics of SiO2 on silicon are controlled by oxidant diffusion
and Si/SiO2 interface chemical reaction.

• This simple Deal-Grove model has been extended to include 2D effects, high
dopant concentrations, mixed ambients and thin oxides.

• Process simulators today include all the physical effects (and more) and are
quite powerful in predicting oxidation geometry and properties.

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