I.

Oxidation Process

Hyungjin Kim
EE, Inha University
(hkim@inha.ac.kr)

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 Oxidation vs Deposition

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 I. Oxidation Process

1.Oxidation and Redistribution

2.Oxide Property and Applications

3.C-V Curves and Measurement of Oxide Properties

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Chapter 1. Oxidation and Redistribution

1. Oxide formation depending on temperature

1) T < 200 ℃ :

• anodization : ethylene glycol(C2H4(OH)2) + KNO3

• vacuum deposition : SiO2 , Si + O2
• sputtering : coverage, stoichiometric

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 2) 250 ℃ < T < 600 ℃ : SiH4
• ~400 ℃ SiO2 for passivation
• doped SiO2 by B2H6 , PH3

3) 600 ℃ < T < 900 ℃

• TEOS (tetra-ethyl-orthosilicate, Si(OC2H5)4)
• SiH4 or SiCl4 + CO2

4) 900 ℃ < T < 1200 ℃ : thermal oxidation

• dry and wet, or Cl incorporated oxidation

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2. Thermal oxide formation

1) oxidation by silicon consumption

45 % silicon oxidation → 100 % SiO2

<Silicon consumption for oxidation>

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 2) oxidation furnace

<Electric furnace, tubes and gas

lines for oxidation>

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3) oxidation time vs. oxide thickness

100

2a

111
<Steam oxidation(STH)>

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 <Dry oxidation(STH)>
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 3. Mechanism of thermal oxidation
1) derivation of oxidation equation
For steady state
F1 = F2 = F3
F1 = hG (CG- CS ) --------------- Eq. (1-1)
hG : mass transfer coefficient
C*
Henry law
PG PS
Co = HPS , C* = HPG ---------- Eq. (1-2)
Ideal gas law
CG = PG /kT , CS = PS /kT ------ Eq. (1-3)
 F1 = h (C*-Co)
(h = hG /HkT)
Fig. 1-5 Oxidation mechanism (Deal & Grove)

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 F2 = D(Co - Ci )/Xo (Fick's law)
D : effective diffusion coefficient of O2 in SiO2

F3 = KsCi
Ks : surface reaction speed

Ks X o
C * (1 + )C *
Ci = Co = D
K X,
K 1+
Ks Ks X o
+
------ Eq. (1-4)
1+ s + s o h D
h D

D = f (O2, T, … )

D : small, Ci→0 and Co→C*, F3 →0 : diffusion control

D : large, Ci  Co = C * (1 + K s h) : reaction control

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 oxide growth rate : G
( F : flux of oxidant reaching the SiO2-Si interface)
dX o
G=
dt
dX o K sC *
F=N = ------ Eq. (1-5)
dt Ks Ks X o
1+ +
h D

N : number of oxidant molecules in a unit volume of oxide

In oxide, 2.31022 SiO2 molecules/cm3

for dry oxidation

N=2.31022 O2 molecules/cm3
for wet oxidation
N=22.31022 H2O molecules/cm3

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 from eq. (1-5), Xo2 + AXo=B (t+) ------------------- Eq. (1-7)

X i + AX i
2

where = , X i = X 0 (0)
B
2 DC *
A = 2 D(1 K s + 1 h) , B =
N

Xo  t +  1
 Eq. (1-7) = 1 + 2  2
−1
A2  A 4 B 

1) t >> A2/4B , t >>

X o = Bt , B : parabolic growthconstant
2

2) t +  << A2/4B
B B
Xo = (t +  ) , : linear growth constant
A A
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 2) comparison of experimental data

• difference between dry and wet oxidation

solubility(H2O) in SiO2 ≈ 103  solubility(O2)
• effect of initial oxide
• grow rate of Cl incorporated case
HCl + O2 -> H2O : effect on A and B
Cl incorporation : effect on D

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 3) activation energy
• parabolic growth

•
• Ea (dry)=28.5 kcal/mol
• ~ Ea (O2 in quartz)=27 kcal/mol
• Ea (wet)=16.3 kcal/mol
• ~ Ea (H2O in quartz)=18.3 kcal/mol

•
<Parabolic growth constant and activation energy>

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 •linear growth

Ea (dry) = 45.3 kcal/mol


Ea (wet) = 46.0 kcal/mol
≈ Si-Si bonding energy
→ depends on Ks

<Linear growth constant and activation energy>

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 4. Impurity redistribution

impurity conc. in Si
1) segregation coefficient (m) = impurity conc. in SiO2

2) diffusion constant (D)

DSiO2>> DSi → not depending on m ( e.g. boron )

3) speed of moving boundary (B/D)

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 <Redistribution of B and P in Si>

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 <Redistribution of B during <Redistribution of P during
thermal oxidation> thermal oxidation>

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Chapter 2. Oxide Property and Application
1. Oxide property
1) oxide property
<Properties of silicon oxide>
breakdown etch rate
formation method density (g/cm3)
field (MV/cm) (Å /sec)
anodization 1.80 5.220.0 40 55
sputtering 2.20 6 10 6 8
TEOS CVD 2.09  2.15 2 8 10 20
CO2 CVD 2.30 5 6 10 15
thermal oxidation 2.24 6.8 9.0 5
silica glass 2.20 2 5 5

Note 1) etch solution ; 10:1 HF (NH4F : HF =10:1)

2) TEOS : Si(OC2H5)4 , tetra-ethyl-ortho-silicate, or equivalently tetra-ethoxy-silane.

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 2) factors on oxidation grow rate (G)

• orientation

• wet oxidation

G[111] > G[100] for T < 900℃

G[111]  G[100] for T > 900℃

It relies on B/A (linear growth rate) at low temperature

and B (parabolic growth rate) at high temperature.

• dry oxidation

always G[111] > G[100]

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 • surface damage

• doping concentration
C(P) > 11020 atoms/cm3
→ large G for low temp. wet oxidation
→ large Ks due to silicon structure change

• oxidation through doped oxide

→ enhance G by increasing B
(especially B-doped oxide)

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 oxide thickness:
0.7 mm

oxide thickness:
0.2 mm

<Oxide thickness of 700 ℃ steam oxidation after various P-predeposition>

Note a) 900 minutes wet oxidation at 700 ℃

b) 35 ppm and 2450 ppm are corresponding to 1.75×1018 atoms/cm3
and 1.23×1020 atoms/cm3, respectively.

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 <B-influence on silicon oxidation>
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3) properties
• thickness
✓ UV-visible photospectrometer, ellipsometer, color chart
• refractive index
✓ ellipsometer
✓ depends on stoichiometric composition
✓ SiO2 (1.46)  Si(3.75)
• density
✓ wafer weight, area and thickness after oxidation
✓ structure defects of oxide
• pin hole
✓ density change
✓ diffusion through pin hole
✓ decrease of breakdown voltage

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 • etch rate
✓ oxide structure and composition

<Etch rate depends on oxides>

(etch solution is HF:HNO3:H2O = 15:10:100)

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 2. Applications of oxide
1) diffusion masking material

2) passivation layer

3) resistive layer( r ≈ 1018 ·cm)

4) doping source

5) gate oxide(gate capacitor)

gate length/oxide thickness :

1 mm/250 Å, 0.5 mm/150 Å, 0.2mm/70 Å, 0.1 mm/30 Å

6) field oxide

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LOCOS (LOCal Oxidation of Silicon)

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LOCOS (LOCal Oxidation of Silicon)

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STI (Shallow Trench Isolation)

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- Thermal oxide - CVD oxide
:Gate oxide, PSG (pre-dep. oxide for STI, ILD, IMD, Passivation
poly Si doping)

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Chapter 3. C-V Curves and
Measurement of Oxide Properties
1. C-V curves

<MOS capacitance vs. C-V curve>

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 1) parameter from C-V measurement :
• dielectric constant of Si and SiO2
• capacitor area
• oxide thickness
• impurity profile in Si
• threshold voltage of MOS capacitor

2) C-V curve

Cox C Si

CoxCSi  ox  Si 2 Sis
Cmin = Cox = , CSi = , Xd =
Cox + CSi Tox Xd qN a

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 - CFB : flat band capacitance
- Cmax : maximum capacitance
- VT : threshold voltage
- Xmax : maximum depletion
width
- deep depletion
- C-V depending on frequency

<C-V curve vs. depletion width>

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 2. Interface charge and C-V curve

<Charges in oxide and oxide/silicon interface>

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Table 3-1 Interface charge system

Type Charge Density

fixed oxide charge Qf Nf
interface trapped charge Qit Nit
mobile oxide charge Qm Nm
oxide trapped charge Qot Not

1) effect due to the mobile charge (Qm)

• kind : Na+, Li+, K+
• charge : 1010∼1012 charges/cm2
• contamination source : gas, ware, chemical, wafer, evaporation, DI water

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 (a) 300 ℃, mobile charge movement by (+) bias

(b) 300 ℃, mobile charge movement by (±) bias

<C-V curve change due to positive ion movement>

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 2) HTB (high temperature bias)

• temperature : 250∼350 ℃
• electric field < oxide breakdown field (1∼10 MV/cm)
• time : 5 minutes

Note : ① initial C-V → (+) stress and cooling

→ 2nd C-V → (-) stress and cooling
→ 3rd C-V (total 30 minutes)
② light irradiation for easy movement of minority carrier

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 3) calculation of Qm and Nm

[charges/cm2]

☞ minimizing Qm : gettering

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 4) fixed oxide charge Qf and C-V
• no change by electric field.
• Qf [100] < Qf [110] < Qf [111]
• origin of Qf : Si dangling bond
• C-V curve shift between theory and after (-) stress : -VFB

(charges/cm2)

• minimizing Qf : anneal (gas, temperature, cooling speed)

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 <Formation of fixed oxide charge during oxidation>

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 5) Qit and C-V

<Effect of interface charges on C-V curve of silicon MOS capacitor>

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 ☞ surface trap level in silicon band gap

<Distribution of interface trapped charges at silicon–oxide interface>

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 6) interface trapped charge Qit in Si band gap
☞ origin of Qit?
• Si-O imperfection
• strong field
• moving particle(cosmic ray)

☞ minimizing Qit : N2 anneal at 350∼500 ℃

- 450℃ H2(25%) + N2(75%) forming gas anneal
- 2Al + 3H2O = Al2O3 + 3H2
H2 + 2Si = 2 Si-H

☞ Summary
In order to reduce interface charges;
• prevent contamination
• avoid radiation exposure
• anneal under N2/H2 atmosphere
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