Thermal Oxidation – Basic concepts

• SiO2 and the Si/SiO2 interface are

the principal reasons for silicon’s
dominance in the IC industry.
• SiO2:
‒Easily selectively etched
using lithography.
‒Masks most common
impurities (B, P, As, Sb).
‒Excellent insulator (ρ > 1016
Ωcm, Eg > 9 eV).
‒High breakdown field (107
Vcm-1)
‒Excellent junction
passivation.
‒Stable bulk electrical
properties.
‒Stable and reproducible
interface with Si.

1
Basic process for the oxidation

Oxidation process takes place at the Si/SiO2 interface.

Silicon oxidation therefore occurs by the inward
diffusion of the oxidant, rather than the outward
diffusion of silicon.

Oxidation involves a volume expansion

because of the room needed for the oxygen
atoms. The oxide would like to expand by
30% in all 3-D to accommodate the oxygen
atoms. Because the silicon substrate prevents
expansion in two directions, the only option is
for the oxide to expand upward. The volume is
thus accommodated by a 2.2 times upward
expansion of the oxide compared to the
volume of the Si oxidized.

2
 Cross-section pictures

Oxide

Silicon

• SiO2 is amorphous even though it

• Oxidation involves a volume grows on a crystalline substrate.
expansion (~ 2.2X).
• Especially in 2D and 3D structures,
stress effects play a dominant role.

3
 Oxidation system

• Oxidation systems are conceptually very simple.

• In practice today, vertical furnaces, RTO systems and fast ramp furnaces all find use.

4
Horizontal tube furnace

5
Vertical tube furnace

• Small footprint
• Good for the increase of the wafer size
• Excellent temp. uniformity
6
Rapid thermal oxidation
Temp.
RTP (Single Wafer)

Furnace (Batch)

Time

• Single wafer type (low

throughput)
• Small thermal budget
• Needs accurate temp.
measurement and
control

7
 Oxide Thickness Characterization (I)
Color chart
• Color Chart
- Compare SiO2 wafer with the reference
color chart
- Periodic repetition of color with
thickness
- No information for thin oxides
- Not accurate measurement method

8
 Oxide Thickness Characterization (II)

• Nanospec®
- Uses monochromatic light and measures the reflected light interference
- Reliably works for film thickness over 10nm
- Needs refractive index
φ
n0

xo β n1

n2
Substrate

9
 Oxide Thickness Characterization (III)
• Ellipsometer
- Polarization change occurs when the
light is reflected from or transmitted
through a medium
- Polarization changes are a function of
optical properties (thickness and
refractive index)
[Link]

10
 Oxide Thickness Characterization (IV)
• High Resolution TEM
- Most accurate measurement technique
- Destructive method (not useful for in-line monitoring)
- Needs sophisticated sample preparation and high cost

Ref) Mark Bohr, “Intel’s 90

nm Process Starting High
Volume Manufacturing,”Intel
Developer Forum, Sep. 16,
2003

11
C-V Measurements

• C-V measurement : the most powerful

tool to characterize SiO2 and the Si/SiO2
interface.

• Electric field lines pass through the

“perfect” insulator and Si/SiO2 interface,
into the substrate where they control
charge carriers.

• Accumulation, depletion and inversion

result.

12
 C-V measurements

• HF curve - inversion layer carriers cannot be generated fast enough to follow the AC signal
so Cinv is Cox + CD.
• LF curve - inversion layer carriers follow the AC signal so Cinv is just Cox.
• Deep depletion - “DC” voltage is applied fast enough that inversion layer carriers cannot
follow it, so CD must expand to balance the charge on the gate.

• C-V measurements can be used to extract quantitative values for:

1. tox - oxide thickness
2. NA - the substrate doping profile
3. Qf, Qit, Qm, and Qot - oxide & interface charges.
• See text for more details on these measurements.
13
Oxide Charges

 Interface-state charge Qit

 originated from structural defect related to the oxidation process, metallic impurities, or
bond breaking processes.

 located at the Si/SiO2 interface with energy states in the silicon forbidden bandgap
and which can exchange charges with silicon in a short time.

 Because interface-state levels are distributed across the silicon bandgap,

Dit ( interface-state density ) is defined as
1 dQit 2
Dit = ( # of charges / cm ⋅ eV )
q dE
2
 Order of 1010/ cm ⋅ eV.

14
 Oxide Charges

 Interface-state charge Qit (Continued)

 C-V and G-V are typically used to determine the Qit.

 A low temperature hydrogen anneal ( post-metallization anneal ) is effective in
reducing Qit.
⇒ usually in forming gas (H2-N2) in the temperature range of 350 ~ 500°C

 Oxide trapped charge Qot

 positively (hole) or negatively (electron) trapped charge in the bulk oxide

 associated with defects in the SiO2, and may result from X-ray radiation or hot electron
injection.
 can be annealed out ( not perfectly )
 range from 109 ~1013 /cm2
 Trapping and detrapping processes cause hysteresis in C-V curve.

15
 Oxide Charges

 Fixed oxide charge Qf

 Originated from nonstoichiometric region (strained region) of SiO2 near the Si/SiO2
interface (SiOx where 1 < x < 2 )
 Immobile under an applied electric field. ( cannot be charged or discharged )
 For electrical measurement, Qf is considered as a charge sheet at the Si/SiO2
interface. ( typically measured by ∆VFB in C-V curve. )
 Ranged from 1010/cm2 ~ 1012/cm2 depending on oxidation and annealing conditions as
well as silicon wafer orientation.
1) orientation dependence : Qf (100) < Qf (111), relating to the number of available
bonds per unit area of silicon surface.
2) the last high temperature thermal treatment determines Qf
( Usually, higher temperature produces lower value of Qf )
a. fast cooling from high temperature oxidation
⇒ rapid cooling prevents oxidation at low temperature
b. when low temperature oxidation is inevitable (e.g. very thin gate oxide
formation ), in-situ subsequent high temperature annealing in an inert gas
ambient is to be added.

16
 Oxide Charges

 Mobile ionic charge QM

 attributed to alkali ions such as sodium, potassium, …. and heavy metals

 range from 1010 ~1012 /cm2
 related to the processing environment, i.e. cleanliness of the oxidation process
including such components of the process as :
a) the furnace tube,
b) processing chemicals,
c) oxidizing ambient,
d) gate electrode material,
e) wafer handing, and so on.

 For most recent device application, all sum of these oxide charges should be
kept to the low 1010 cm-2 regime.

17
 Thermal Oxidation of Silicon

 Because a silicon surface has a high affinity for oxygen, an oxide layer rapidly forms
when silicon is exposed to an oxidizing ambient .

 There are two basic chemical reactions in describing the thermal oxidation of silicon ;

 Dry oxidation : Si (solid) + O2 → SiO2 (solid) …………… (1)

 Wet oxidation : Si (solid) + 2H2O (steam, or water vapor)

→ SiO2 (solid) + 2H2 …………… (2)

O2 or H2O
 Oxidation proceeds by the diffusion of
the oxidizing species through the
dox (oxide
oxide to the Si-SiO2 interface, where
thickness )
the oxidation reaction occurs. 0.44 × dox

Original
surface Silicon
 Volume ratio =

oxide thinkness under the original silicon surface

× 100 % = 44%
total thickness of oxide
18
 Deal & Groove Model

 The oxidizing species are transported with flux ;

 F1 : from the bulk of the gas to the gas/oxide interface

 F2 : diffusion across the existing oxide toward the silicon
 F3 : reaction with silicon at oxide/silicon interface

 At steady state : F1 = F2 = F3

 F1 = hG (CG − C S ) …………… (3)

where hG is the gas-phase mass-transfer coefficient.

 F1 is linearly approximated by assuming that the flux of oxidant

is proportional to the difference between the CG and CS.

19
 To relate the equilibrium oxidant concentration
in the oxide to that in the gas phase,
Henry’s law is involved.
CO : equilibrium concentration in the oxide
 CO = H ⋅ p S ……… (4) at the outer surface
C* : equilibrium bulk concentration in the
 C * = H ⋅ pG ……… (5) oxide
pS : partial pressure in the gas adjacent to
 For the ideal gas, the oxide surface
pG : partial pressure in the bulk of the gas
pG H : Henry’s law constant.
 CG = ……… (6)
kT hG : the gas-phase mass-transfer
pS ……… (7) coefficient
 CS =
kT
 From Eq. (4) ~ (7), we can rewrite Eq. (3) as

 F1 = h(C * −CO ) ……… (8)

hG
where, h=
HkT

20
 Diffusion of oxidant across the oxide :
D : the diffusion coefficient
(C − Ci )
 F2 = − D dC = D O ……… (9) dox : the oxide thickness
dx d ox Ks : the rate constant of interface
reaction for silicon oxidation
 Following the steady-state assumption, F2
must be the same at any point within the
oxide, resulting in
(CO − Ci )
F2 = D .
d ox
 The flux corresponding to the Si/SiO2 interface reaction is

 F3 = k s Ci ……… (10)

21
 At steady state, F1 = F2 = F3.
Thus,
C*
 Ci = ……… (11)
k kd
1 + s + s ox
h D
k s d ox
[1 + ]⋅C *
 CO = D ……… (12)
k kd
1 + s + s ox
h D

 When D is small or dox is large, Ci → 0, CO → C*.

( oxidant supply to the Si/SiO2 interface is not enough. )
⇒ diffusion-controlled ( or diffusion-limited )

C*
 When D is large or dox is small, Ci = CO →
( an abundant supply of oxidant is k
1+ s
provided at the Si/SiO2 ) h
⇒ reaction-controlled ( or reaction-limited )

22
 Oxidation rate :

dd ox ksC *
 N1 = F3 = k s Ci = ……… (13)
dt k kd
1 + s + s ox
h D
N1 :the number of oxidant
 Initial condition : when t = 0, dox = di. molecules incorporated into a
( assuming that an oxide may initially unit volume of the oxide layer.
be present )

 From Eq. (13), the famous “linear-parabolic relationship” is derived.

2
 d ox + A ⋅ d ox = B (t + τ ) ……… (14)

Where, 1 1
A = 2 D( + ) ……… (14a)
ks h
2 DC * “τ” represents a time shift to
B= ……… (14b)
N1 account for the presence of
the initial oxide layer di .
d i2 + Ad i
τ= ……… (14c)
B 23
 From Eq. (14),
1
A  t +τ 2
 d ox /( ) = 1 + 2  − 1 ……… (15)
2  A / 4B 

 For long time oxidation ( t >>τ ),

2
d ox ≅ B ⋅t ……… (16)

 For short time oxidation ( t+τ << A2/4B ),

B
d ox = (t + τ ) ……… (17)
A

B : parabolic rate constant

B ks h C *
=(
: linear rate constant ⋅ )
A ks + h N1

24
 Even though D of water < D of oxygen in oxide,
B for wet oxidation is substantially large than for dry oxidation.
⇒ because C* for wet oxidation is three orders of magnitude greater than for dry
oxidation.
C* can be calculated by Eq. (14b) if we measure B.
( C* for O2 : 5.2 × 1016 cm-3 at 1000°C,
for H2O : 3.0 × 1019 cm-3 at 1000°C )

25
SiO2 Growth Kinetics Models
A. Deal Grove Model

26