EECE 5141C/6041C:

Microfabrication Lab for

Semiconductor Devices and MEMS

2. Silicon Oxidation
Tao Li

Spring 2023
Acknowledgements: This lecture is partly based on Prof. Chong Ahn’s
previous course notes.

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Process Examples

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 Silicon
• Second most abundant element on earth
• Hard and grayish element, commonly found as silica (SiOx)
• Three material structures: single crystal, polycrystalline
(polysilicon), and amorphous (a-Si or α-Si)
• Diamond cubic crystalline structure
 Lattice constant: 2.35 Å, density: 5.02x1022 atoms/cm3
• Crystal orientations: (100), (111), (110) Silicon ingot grown by
• Czochralski (CZ) process for growth of single crystal silicon Czochralski process

• Intrinsic (pure, undoped) and doped (n type or p type)

silicon
• Wafer sizes
 1”, 2”, 3”, 4”, 6”, 8”, 12” diameters
 275 µm to 775 µm standard thicknesses,
larger thickness for larger diameter

Silicon wafers of various sizes

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Silicon Oxide
• Oxide of silicon (SiO2): random network of silicon and oxygen atoms
• It has excellent properties, used in IC industry as high quality dielectric
material and as diffusion mask of common silicon dopants (B, P, and As)
• Fabrication methods:
 Thermal growth
 Deposition by chemical vapor deposition (LPCVD or PECVD) or sputtering
• Properties:
 Relative dielectric constant: 3.9
 Index of refraction: 1.46
 Breakdown field: 6 x 108 V/m
 Melting temperature: ≈1700ºC
 Thermal expansion coefficient: 5 x 10-7 /K
• Usage:
 Insulator: gate oxide and field oxide for transistors
 Etching or ion doping mask
 Microstructure
 Sacrificial layer

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 Silicon Oxide Usage
Oxide

(100) Si

Etched cavity
Insulator: gate oxide and field Etching mask
oxide for MOS transistors
Ion Implantation
Oxide bridge
Oxide
p++
Drive-In
Si Si
Microstructure Ion doping mask

Poly-Si

Oxide Suspending
oxide
Si structure Si

Sacrificial layer
H. Baltes, Swiss Federal Institute of Technology

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Thermal Oxidation
• Wafers first cleaned to remove organics and ions (Na+ etc.), and
then placed inside a furnace
• Furnace should have accurate temperature control, usual target
range of 900-1200ºC
• Carrier gas (usually nitrogen) is flown through the furnace. O2 is
introduced by the carrier gas through
 Liquid sources (steam)
 Gas sources

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 Thermal Oxidation Growth Mechanism
• Chemical reaction
 Dry oxidation: Si (Solid) + O2 = SiO2 (Solid), slow growth but high
quality, suitable for growing oxide of a few 100-1000 Å thickness
 Wet oxidation: Si (Solid) + 2H2O = SiO2 (Solid) + 2H2, fast growth, still
high quality but less dense and quality than dry oxide, suitable for
growing oxide of >5000 Å thickness
• Deal-Grove Model: Reaction and diffusion mechanism can describe
the kinetic of silicon oxidation
1. O2 must be transported from the bulk of the gas to the oxide-gas
interface
2. O2 must diffuse across the oxide layer already present
3. O2 must react at the silicon surface to create the SiO2 layer

O2 Diffusion
Silicon

Reaction

Silicon oxide

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Deal-Grove Model

SiO2

Si Si
O2 O2

Mass transfer Diffusion Reaction

Reaction only Diffusion & Reaction

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 Flux Continuation
• The oxidizing species
 are transported from the bulk of the gas phase to the gas-oxide
interface with flux F1.
 F1 = flux of oxidant from the gas to the surface (or # of molecules

crossing a unit area in unit time)

 diffuse across the existing oxide toward the Si with flux F2 (Fick’s
Law).

 react at the oxide-silicon interface with flux F3.

• Flux continuation: F1 = F2 = F3

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Oxide Growth Model

4𝐵
𝑥 0.5𝐴 1 𝑡 𝜏 1
𝐴

where
A, B: temperature dependent constants (Deal/Grove rate constants)

𝜏 : initial factor

xi: initial thickness of oxide

t: oxidation time

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 Oxide Growth Model
• Limiting Cases

 For short oxidation times (thin oxide), 𝑡 𝜏 𝐴

4𝐵

𝐵
𝑑 𝑡 ≅ 𝑡 𝜏
𝐴
Linear regime (reaction-limited) when d < 300 Å

 For long oxidation times (thick oxide), 𝑡 𝜏 and 𝑡 𝐴

4𝐵

𝑑 𝑡 ≅ 𝐵𝑡

Parabolic regime (diffusion-limited) when d > 300 Å

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Deal-Grove Rate Constants

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 Deal-Grove Rate Constants

After Deal and Grove

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Thermal Dry Oxidation Rate of (100) Si

After Berger
and Donavan

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 Thermal Wet Oxidation Rate of (100) Si

After Berger
and Donavan

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Thermal Wet Oxidation Rate of (100) and (111) Si

Oxide thickness
vs. oxidation time
for silicon in wet
ambient at 640 Torr

After Deal &

Grove

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 Thickness
• Oxidation Thickness
 Mole # (# of atoms) of Si in Si = mole # (# of atoms) of Si in SiO2
𝑊𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑆𝑖 𝑐𝑜𝑛𝑠𝑢𝑚𝑒𝑑 𝑊𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑆𝑖𝑂2
𝑀𝑜𝑙𝑒 𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑆𝑖 𝑀𝑜𝑙𝑒 𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑆𝑖𝑂2
𝐴 𝑑2 𝜌 𝐴 𝑑 𝜌
28.0855 60.08
𝑑2 28.0855 · 𝜌
0.44, 𝑤ℎ𝑒𝑟𝑒 𝜌 2.2𝑔/𝑐𝑚3, 𝜌 2.32𝑔/𝑐𝑚3
𝑑 60.08 · 𝜌
 d1=0.56d and d2 = 0.44d, where d is total thickness grown
 Volume of oxide formed is 2.27x the volume of silicon used

d d1
d2
SiO2 (Area = A)

Silicon d1 = 0.56d
Silicon SiO2 d
d2 = 0.44d
Silicon oxide
Si Original
Original Si surface Si surface

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SiO2 Thickness Characterization

• By ellipsometry: measure index of refraction and thickness of SiO2,
highest accuracy of ≈1 nm

Rudolph
Auto EL III
Ellipsometer
• By spectroscopic reflectometry: Nanometrics Nanospec, etc.
• By surface profilometer: using a stylus to measure oxide steps
created by etching portion of wafer, can reach 3-5 nm accuracy
• By color: Color 1 2 3 4
Grey 100 Thickness in Å
Tan 300
Brown 500
Blue 800
Violet 1000 2800 4600 6500
Blue 1500 3000 4900 6800
Green 1800 3300 5200 7200
Yellow 2100 3700 5600 7500
Orange 2200 4000 6000
Red 2500 4400 6200
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 Other Fabrication Approaches for SiO2 – LPCVD
• Chemical vapor deposition (CVD) can deposit thin films from gas phase
• Low pressure CVD (LPCVD):
• High deposition temperature (450-800ºC)
• High film quality (not as high as thermally grown silicon oxide film, less dense)
• Excellent control of thickness, high uniformity across wafers in batch
• Excellent step coverage, conformal film
• Thickness can vary between <1 µm to >10 µm, deposition rate of tens of Å/min
• Can process large batch of wafers simultaneously

LPCVD reactor
LPCVD furnace banks

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Other Fabrication Approaches for SiO2

• Plasma enhanced CVD (PECVD)
• Reaction energy from a plasma excited from RF field
• Lower deposition temperature (200-400ºC or even 100ºC in some cases)
• Can be deposited on metal film on wafer
• Usually faster deposition rate, 10-100 nm/min
• PECVD film quality very good, but not as good as LPCVD films
• Good thickness uniformity across individual wafer
• Single wafer or small wafer batch
• Physical vapor deposition (PVD): Sputtering

Nano-Master PECVD
PECVD reactor system

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