Si wafer cleaning

Hyeongtag Jeon

Division of Materials Science and Engineering

Hanyang University

Semiconductor Materials Laboratory1

 Wafer Cleaning

Objective of wafer cleaning :

to remove the particulates and impurities on the
silicon surface without damaging or altering
the substrate surface.

Importance of clean substrate surface :

chemical contaminants and particulate impurities
affecting device performance, reliability and
product yield of silicon circuit.

Semiconductor Materials Laboratory2

 Wafer Cleaning

Requirements for Si wafer cleaning process

1. Effective removal of all types of surface contaminants
2. No etching or damaging Si and SiO2
3. Using the contamination-free and volatilizable chemicals
4. Relatively safe, simple, and economical
for production application
5. Ecologically acceptable, free of toxic waste products
6. Implementable by a variety of techniques

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 Wafer Contamination

1. Organics
2. Particles
3. Native Oxides
4. Chemical Oxides
5. Metallic impurities and etc

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 Wafer Contamination

Organics

Sources : lubricants, coolants, cutting oils, fatty materials,

airborne particles, detergents, organic residues
Contamination : most commonly found after evaporation
of organic solvents
Effects : preventing effective cleaning or rinsing
impairing good adhesion of deposited films
forming deleterious decomposition
products during heating (ex. SiC)

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 Wafer Contamination

Particles

Sources : in air or liquid chemicals, adsorbed gases

or vapors, factory operators, container, etc.
Contamination : most commonly generated during
the processing
Effects : causing blocking or masking of wafer processes
leading to pinholes, micro-voids, or defects
acting as a device killer
(if 1/10 of feature sizes)

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 Wafer Contamination

Native oxides
Sources : oxygen in the air, DI water, or liquid chemicals
Contamination : always presence of oxide layer on Si wafer
Effects : preventing the epitaxial growth of thin films
trapping of the inorganic contaminants in oxides

Chemical oxide
Sources : chemical solution during wet cleaning process.
more uniform layer than native oxide

It is used as the protecting layer of other contaminants

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 Wafer Contamination

Metallic impurities
Sources : metallic impurities in the chemicals or PR residues
process equipment(steel), metal tweezer,
fabrication processing
2
)

1.0E+13
Concentration of metallic impurities(atoms/cm

1.0E+12

Resist ashing
1.0E+11 Dry etching
Ion implantation

1.0E+10

1.0E+09
Cu Fe Ni

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 Wafer Contamination

Effects :
Diffuse into Si substrate during heating, and act as trap centers in Si band gap
Decrease minority carrier lifetim
Degrade the electrical characteristics
(leakage currents , breakdown voltages )
Lower the device yields and reliabilities

Control of metallic impurities

below 1010atoms/cm2

An example of contaminations
on Si or metal surfaces

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 Wafer Contamination

Ultraclean Surface

1) Particle free
2) Metallic contaminants free
3) Organic contaminants free
4) Native oxide free
5) Surface microroughness free
6) Completely hydrogen terminated
7) Moisture molecule free

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 Cleaning Methods
Wet Cleaning
RCA cleaning
Ohmi cleaning
IMEC cleaning
SC1, SC2 etc

Dry Cleaning
Plasma cleaning
UV ozone cleaning
Vapor cleaning

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 Wet Cleaning

Wet chemical cleaning methods

Immersing method into the liquid chemicals
Currently the most widely used cleaning method

Mechanism of wet chemical cleaning

1) Liquid cleaning
: physical dissolution and/or chemical reaction dissolution

2) Chemical etching
: chemical transformation of contaminants into soluble species

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 Wet Cleaning

Mechanism of Wet Chemical Cleaning

Mechanism of hydrogen termination (wet)

HF Si cleaning Si-F bond 6 eV (strongest simple bond)

SiO2 + 4HF SiF4 + 2H2O
Si-H bond ~ 3.5 eV

thermodynamically, stable F- termination

high polar nature of Si-F bond cause

bond polarization of Si-Si back -bond.

allow HF attack and result in Si-H bond.

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 Wet Cleaning

Hydrophilic surface Hydrophobic surface

HF cleaning

Native/chemical oxide H-terminated surface

Contact angle 10 Contact angle 60

High surface energy Low surface energy
Poor passivation Good passivation
Good adhesion to H2O Poor adhesion to H2O

Good wetting Poor wetting

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 Wet Cleaning
RCA
H2SO4/H2O2 (4 : 1, 120-150)
UPW rinse (RT)
HF / H2O (0.5%, RT)
UPW rinse (RT)
NH4OH / H2O2 / H2O
(0.05:1:1, 80-90)
UPS rinse (RT)
Hot UPW rinse (80-90)
UPW rinse (RT)
HCl/H2O2 /H2O (1:1:6, 80-90)
UPW rinse (RT)
HF / H2O (0.5%, RT)
UPW rinse (RT)
Ohmi method
O3 / H2O (10ppm, RT,
metallic, organics)
HF / H2O2 / H2O (0.5%HF, 1%H2O2) +
surfactant + megasonic
(RT, oxide, metallic)
Dilute HF cleaning (RT, H-termination)
UPW shower rinse (RT)
UPW parallel down-flow rinse +
megasonic (RT)
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 Wet Cleaning

RCA standard cleans

SC-1 NH4OH : H2O2 : H2O = 1 : 1 : 5, 5min, 70-85
dissolving and forming a new native oxide
removing the particles and organics
fast decomposition of H2O2 and NH3 at above 80
creating microroughness on the Si surface
lowering the concentration of NH4OH

SC-2 HCl : H2O2 : H2O = 1 : 1 : 5, 5min, 70-85

removing the metallic impurities and
insoluble metal hydroxides
no etching oxide or Si surface

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 Wet Cleaning

HF acid cleans
DHF HF : H2O = 1 : 10 to 100, RT, 10 sec to 1 min
removing the SiO2 films and silicate glasses
(ex : phosphosilicate or borophosphosilicate)
changing the surface (hydrophilic to hydrophobic)
Si surface : H- terminated (or passivated)

BHF(BOE, buffered oxide etch) HF : NH4F = 1 : 7

used for removing the oxides instead of DHF
HF2- : major etchant species
maintaining the concentration of etchant
stabilizing the etching rate and preventing PR liftoff in HF

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 Wet Cleaning

H2SO4 acid clean

H2SO4 : H2O2 = 4 : 1, 10min, at 120
referred to piranha etch, or Caros acid
removing the organic contaminants

Choline solution clean

C5H14NO, dilution or adding surfactant & H2O2
trimethyl-2-hydroxyethyl ammonium hydroxide
strong and corrosive base and Si etchant
excellent wetting for Si after adding H2O2
similar effect to SC-1 (removing PR or particles)

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Energy Level = - (4.44 +P RED) M++e-M
Electro negativity Standard Redox Energy level
Element
(Pauling) Potential [ V vs. NHE] [ eV]
Au 2.4 1.68 - 6.12
Pt 2.2 1.19 - 5.63
Ag 1.9 0.7991 - 5.2391
Hg 1.9 0.789 - 5.229
Cu 1.9 0.337 - 4.777
Si 1.8 0.102 - 4.542
Pb 1.8 - 0.1288 - 4.3112
Sn 1.8 - 0.1375 - 4.3025
Ni 1.8 - 0.228 - 4.212
Fe 1.8 - 0.440 - 4.00
Zn 1.6 - 0.7631 - 2.8669
Al 1.5 - 1.662 - 2.778
Mg 1.2 - 2.37 - 2.07
Ca 1.0 - 2.84 - 1.60
Na 0.9 - 2.7141 - 1.726
K 0.8 - 2.925 - 1.515

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 Chemical adsorption of Cu
Potential - pH Diagram
for Cu-Water System on Si wafer
2Cu2 + + Si + 2H2O = 2Cu + SiO2 + 4H+
2 E=1.21V
Dissolution
1.5 Cu2+ Cu(OH)2

1
The anodic oxidation reaction
E, volts

0.5
Si + 2H2O = SiO2 + 4H+ + 4e
The cathodic reduction reaction
0
2Cu2 + + 4e = 2Cu
-0.5
Cu
-1
Cu2+ is adsorbed chemically
-1.5 by exchanging electrons.
0 2 4 6
pH
8 10 12
SiO2 forms between interface
Cu - water Poubaix diagram(25C) of Si and Cu.

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Mechanism of adsorption and removal of Cu

Cu a) Cu adsorption on Si wafer
Si SiOx SiOx between Cu particle and Si
CuOx
SiOx
Cu
b) The oxidation of Cu and Si
Si wafer

MIP c) The removal of Cu with HF

Cu

Si Metal Induced Pit

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 Wet Cleaning

Characterization after wet cleaning

1) Residual amounts for ultra-trace impurities on Si surface
SIMS : DL (107 to 108 atoms/cm2)
TXRF : DL (1010 atoms/cm2)
2) Volume-sensitive methods for bulk contamination analysis
SPV : measuring the minority carrier diffusion length
DLTS : measuring Fe concn. or the minority carrier lifetime
3) Atomic structure or morphology, and surface composition
XPS : observing the chemical bonding of native oxide or
impurities
AFM : observing the surface roughness
Angle resolved light scattering
4) STM, LEED, RHEED, UPS, etc.

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 Wet Cleaning
WET CLEANING PROCESS
ADVANTAGE
Easy to wash by water after the process
Residues after drying can be avoided by di-
water and suitable drying methods
The liquid used is not flammable.
A wide variety of chemical solutions are
available
It's cheap.
It is effective for both organic and non-organic
removal
The selective removal ability is relatively good
DISADVANTAGE
Drying is slower than organic chemicals and
there is a possibility that residues will remain
The removal efficiency of some organic
substances is lower than that of organic
solvents.
Most liquid chemicals are dangerous toxic
substances
Disposal is costly
It is difficult to use in a vacuum system
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 Dry Cleaning

Dry Wafer Cleaning

cleaning method carried out in the gas or vapor phase
Requirements of dry wafer cleaning technology
1) Can remove heavy, transition, and alkali metals
which are the most difficult to volatilize
2) Not roughen the semiconductor surface
nor generate defects in the oxide
3) Not generate solid residues that remain on the cleaned surface
4) Must have high throughput
5) Effective at fairly low temperature
6) Designed to assure compatibility with cluster tool processing
and integrated process
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 Dry Cleaning

Mechanism of Dry Wafer Cleaning

Chemical reaction Chemically
reactive species
Accelerated incident ions
Momentum transfer

Volatile
compounds

Si Si
a) Physical gas-phase cleaning b) Chemical dry cleaning
removal of contaminants : better selectivity and reduce
by momentum transfer between ions a risk of contaminant redeposition
accelerated toward the surface reduce the surface damage
and contaminants species

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 Dry Cleaning

Mechanism of metal contaminants removal

Lift- off Si-Cl Evaporation
Cl radical
M-Cl
Reduced Elevated
pressure temperature

Si
a) Lift off mechanism
- metal chlorides are more volatile
than other metal halides
Si
b) Evaporation mechanism
- due to the random nature of
interactions
- at the elaborated temperature
and reduced pressure

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 Dry Cleaning

Dry cleaning Research Status

GROSS FINE
Organic matter Organic matter
metal oxide
LOW ENERGY
Physicalmethod Sputtering

H2 Annealing
Heating HIGH T/UHV
Oxidation Oxidation HCl MID T/UHV
method GeH4 : H2
Dry
HF : H2O VAPOR
cleaning Weather system HCl : HF : H2O HF : CH3OH

method Uvmethod UV / ozone

UV/ozone
UV/O2 H2O VAPOR
UV/Cl2
UV/HF : CH3OH
UV/NF3 : H2 : Ar
REMOTE
DIRECT PLASMA H2
PLASMA O2 REMOTE REMOTE ECR PLASMA
Plasma method
REMOTE PLASMA O2 PLASMA HCl NF3 or H2
PLASMA O2 REMOTE
PLASMA NF3 : H2

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 Dry Cleaning

Categories of dry wafer cleaning

1) Physical interactions
2) Physically-enhanced chemical reactions
3) Chemical thermal reaction
4) Mechanical technique
Contaminants removal by dry cleaning
1) Organic contaminants : volatilization, UV/O3 reaction,
remote or downstream oxygen plasma treatment
2) Native and chemical oxide, silicate glasses : chemical etching,
physical sputter etching, low-energy ECR plasma etching
3) Metal and absorbed ions : remote plasma,
photo-induced reaction
4) Particle : vapor etching

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 Dry Cleaning

Photochemically-Enhanced Cleaning
Low pressure vapor UV lamps as the radiation sources
energies required for efficient photolysis
Uniform high intensities for wavelengths (150 ~ 600 nm)

UV/O3 cleaning
Oxidize and volatilize organics from surface
Pre-oxidation surface treatment
Organic removal prior to metallization
Surface carbon and hydrocarbon removal
Strip photoresist
Remove polymer films after RIE process

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 Dry Cleaning

UV lamp
Dry air

Si wafer
H
H C H CO2 + O2 + H2O
O2 O3 + O
oxide
Schematic illustration
Si of the hydrocarbon
removal by UV/ozon

Organic contaminants + h exited organic contaminants (200~300 nm UV)

O2 + h 2O (184.9 nm UV)
O + O2 O3
O3 + h O + O2 (253.7 nm UV)
exited organic contaminants + ( O, O3 ) volatile compounds

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 Dry Cleaning

UV/O3 : (a) The result of oxygen removal by B.S.Krusor (USA)

(b) The result of carbon removal by H.Jeon (Korea)

After UV/O3
as received
treatment

a) b)

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 Dry Cleaning

UV/Cl2 Cleaning
UV exposure in a Chlorine ambient
remove metallic contaminants by volatilization
lift metallic contaminants off the surface
Not enough to remove alkali metals (Ca, Na)
need additional treatment
Not need additional elevated temperature nor reduced pressure
Problem : non-uniform, excessive etching of silicon resulting in
rough surfaces

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 Dry Cleaning

Plasma Enhanced Cleaning

Direct plasma cleaning
- Ion-induced damage of the substrate
Radiation-induced oxide defect
- Metallic contaminants and/or alkali ions penetrate the substrate
recontaminate the substrate
Remote plasma cleaning
- By generating an active plasma in a spatial region
remote from the substrate
- Avoid ion acceleration into the substrate
O2 plasma Remove organic contaminants
HCl : Ar plasma Remove metallic contaminants
Problem of corrosion
NF3 : H2 : Ar plasma Etch native/chemical oxide

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 Dry Cleaning

Remote H2 plasma :
The result of carbon and oxide removal by R.J Markunas (USA)

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 Dry Cleaning
The effect of metallic contaminants removal
by H2 Plasma cleaning
Fe Cr Ni Cu Zn
Initial 387 5.83 35.9 71.6 359
20w 5 min 19.3 0 0 0.941 48.9
40w 5 min 24 2 0 0.638 81

400

300
Initial
200
20w 5 min
100 40w 5 min

0
Fe Cr Ni Cu Zn

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 Dry Cleaning

DRY CLEANING PROCESS

ADVANTAGE DISADVANTAGE

Full-scale cluster tool process Be easy to achieve. Use expensive equipment..

High aspect ratio structure Be advantageous to.

Consideration should be given to control of heavy
metals or transition metals that are not well removed.
Particles are easier to control in gas than in liquid.
It is usually a single-wafer process.
When used in a high temperature process,
Usage of chemical solution and DI water is low. metal impurities may diffuse into the substrate.

It is a safer process than wet cleaning process

The amount of waste solution is small and easy to dispose.

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 Summary and Trend

1970 s RCA cleaning

1980 s Modified RCA cleaning Concentration, temperature,

cleaning solution
1990 s Megasonic adoption

Wet cleaning Dry cleaning

(Ultra clean technology) Vapor phase cleaning Cluster Tool
Ozonized DI water, Plasma cleaning Introduction
upw, Surfactant adding

New cleaning method HF-vapor system System System with O

with reduced chemical H-ECR plasma xidation and Cleaning
usage and cleaning step H-remote plasma Tool

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 Future Direction

Future direction in Wafer Cleaning

1) Use of super-pure chemicals, gases and DI water
2) Cleaner equipment, and fab facilities
Reduce the micro particle
3) Innovative analytical methods
: detecting, measuring, and monitoring ultratrace surface
contaminants and microparticles
4) Fully-automated system and cluster tool process
5) High product, high reliance, space saving, and low cost process
6) General reduction of liquid chemicals and gases
for processing and ecology reasons

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