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Cleaning

75% of Yield loss due


to particles

3-pronged appraoch:
1. Clean Factories
2. Wafer Cleaning
3. Gettering
From Intel
Cleaning

Prof. Milo Koretsky


Chemical Engineering Dept .

1. Clean Factories

Class of the clean room Laminar


Flow

From Middleman

Cleaning

Prof. Milo Koretsky


Chemical Engineering Dept .
2. Wafer Cleaning
• It is important to have clean wafers at all stages of fabrication.
• Cleaning is especially important before any high temperature
process.
• Improper cleaning can result in yield loss and process variability
• Cleaning comprises roughly 1/4 of the IC process steps

Wafers Cleaning
solution

Cleaning

Prof. Milo Koretsky


Chemical Engineering Dept .

Typical Chemicals Involved


Chemical Name

H2O (DI) De-Ionized water


H2SO4 Sulfuric Acid
H2O2 Hydrogen Peroxide
H2O Water
HF Hydrofluoric Acid
NH4OH Ammonium Hydroxide
HCl Hydrochloric Acid
IPA Isopropyl alcohol

Cleaning

Prof. Milo Koretsky


Chemical Engineering Dept .
Si Surfaces
•The chemical nature of the Si surface affects reactivity with contaminants

H HH HH HH H
O O O O O O O O O O O O

Si Si Si Si Si O Si Si O Si Si O Si Si O Si
O O O O O O O O
Si Si Si Si
Si O Si O Si O Si Si O Si O Si O Si
Si Si Si Si
Si O Si O Si O Si Si O Si O Si O Si

Bare Si Silicon oxide Silanol on silicon oxide

Cleaning

Prof. Milo Koretsky


Chemical Engineering Dept .

Generic Contaminated Si Surface


•Air

•Absorbed gas
•Particles
•Nonpolar organics
•Polar Organics
Water •Water
Silicon Oxide •Oxide

Silicon Wafer

Cleaning

Prof. Milo Koretsky


Chemical Engineering Dept .
De-ionized (DI) Water
• Ions are reactive. They can make liquid products from solids. They
can also bond to the solid.
• Normal tap water has many different types of ions.
• If we want to clean wafers without causing any reactions, we can not
use tap water. We need special water which is free of ions.

Tap water De-ionized water


• Ion free water is
called
De-ionized water
or DI water.
Na+
Cl-
F-

Cl-
K+ F-
K+
Na+
Cleaning

Prof. Milo Koretsky


Chemical Engineering Dept .

Relative Strength of Binding Forces Important for


Aqueous Cleaning
Adsorption Type Energy (eV)

Chemical Bonds
Ionic 6-11
Covalent 0.6-7
Metallic 1-3.5

Physical Forces
H bonds <0.5
dipole-dipole <0.2

Despersion <0.4

Cleaning

Prof. Milo Koretsky


Chemical Engineering Dept .
General Scheme - RCA Clean
H2SO4 H2O Rinse H2O : HF H2O Rinse
H2 O 2 Room Temp (10 : 1)
125oC Room Temp
“Sulfuric Clean”; Organics “10 to 1”; Oxide Etch

H2O / NH4OH /H2O2 H2O Rinse H2O / HCl /H2O2


(5:1:1) Room Temp (6:1:1)
80oC 80oC
“SC 1”; Particles “SC 2”; Surface Metals

H2O Rinse H2O : HF H2O Rinse Alcohol (IPA)


Room Temp (100 : 1) Room Temp Dry
Room Temp Room Temp
“100 to 1”; Oxide Etch Wafer dry
W. Kern and D.A. Puotinen, “Cleaning solutions based on hydrogen peroxide in
silicon semiconductor technology,” RCA Rev. 31, 187-206 (1970).
Cleaning

Prof. Milo Koretsky


Chemical Engineering Dept .

Individual Cleaning Processes


H2SO4 H2O Rinse H2O : HF H2O Rinse

• Lets see the purpose of each H2O2


125oC
Room Temp (10 : 1)
Room Temp

of these steps.
H2O / NH4OH /H2O2 H2O Rinse H2O / HCl /H2O2
• Sulfuric Clean(Piranha) (5:1:1)
80oC
Room Temp (6:1:1)
80oC

• Recipe: H2SO4 /H2O2 /125oC


H2O Rinse H2O : HF H2O Rinse Alcohol (IPA)
• Removes: Organics Room Temp (100 : 1)
Room Temp
Room Temp Dry
Room Temp

• Hydrogen peroxide (H2O2) provides the chemical action for the


sulfuric clean. H O H Hydrogen
peroxide
• H2O2 has two oxygens. O (H 2O2)
• It easily gives up one of its oxygen atoms.
H O H product formed by
O O using other oxygen
H (H 2O ) from H2O2
(H 2O2) H
Cleaning

Prof. Milo Koretsky


Chemical Engineering Dept .
Sulfuric Clean (Piranha)
• Action:
• Organics are mainly carbon (C) and hydrogen (H)
• Hydrogen peroxide (H2O2) wants to give up one of its
oxygen atoms. It readily produces CO2( g ) and H2O( l ) on
reacting with organics.
H2O( l )
H O H
H
O O
H O H H H CO2( g )
O O H

Hydrogen
peroxide C C C
(H2O2)
Organic Impurity H O H
O
Cleaning

Prof. Milo Koretsky


Chemical Engineering Dept .

DI Water Rinse
H2SO4 H2O Rinse H2O : HF H2O Rinse
• Recipe: H2O* / Room Temperature H2O2
125oC
Room Temp (10 : 1)
Room Temp

• Removes: Cleaning chemicals H2O / NH4OH /H2O2


(5:1:1)
H2O Rinse
Room Temp
H2O / HCl /H2O2
(6:1:1)

and reaction products from an 80oC 80oC

earlier wet clean. H2O Rinse H2O : HF H2O Rinse Alcohol (IPA)
Room Temp (100 : 1) Room Temp Dry
Room Temp Room Temp

• Action:
• Dissolves chemicals and reaction products
• A DI water rinse may also be used to stop the action of
cleaning chemicals.

Cleaning

Prof. Milo Koretsky


Chemical Engineering Dept .
Oxide Etch
H2SO4 H2O Rinse H2O : HF H2O Rinse

• Recipe: H2O / HF H2O2


125oC
Room Temp (10 : 1)
Room Temp

• Removes: Oxide (SiO2)


H2O / NH4OH /H2O2 H2O Rinse H2O / HCl /H2O2
• Action: (5:1:1)
80oC
Room Temp (6:1:1)
80oC

• HF reacts with SiO2 to


make liquid products. H2O Rinse
Room Temp
H2O : HF
(100 : 1)
Room Temp
H2O Rinse
Room Temp
Alcohol (IPA)
Dry
Room Temp

SiO2( s ) + 6HF( l ) -> H2SiF6( l ) + 2H2O( l )


• The etch rate (or reaction rate of HF with oxide) can be
slowed by adding more water. The lowers the concentration
of HF.
• A DI water rinse is used to stop the action of acid after this
cleaning step.
Cleaning

Prof. Milo Koretsky


Chemical Engineering Dept .

(10:1) Oxide Etch


• The wafer goes through many processing steps before gate oxide
can be deposited.
• A thick layer of poor quality oxide is grown in these steps to help ion
implant.
N-Si N-Si
P-Si

• Now we need to remove this poor quality oxide before we can grow
high quality gate oxide.
• This removal is done in the (10:1) Oxide Etch. A high concentration
of HF is used because we have a lot of oxide.
N-Si N-Si
P-Si
Cleaning

Prof. Milo Koretsky


Chemical Engineering Dept .
(100:1) Oxide Etch: Importance
• The silicon at the bottom of contact holes reacts with oxygen in the
air. It forms a thin layer of oxide. This oxide is called native oxide.
Contact hole
• We want to remove the native
oxide. This allows the metal to Native oxide

make a good contact with the


source and drain.
• The trick here is:
• To remove the oxide at the bottom (native oxide)
• Not to remove much of the oxide from the sides of the contact
holes.
• This removal is done in the (100:1) Oxide Etch. A low concentration
of HF is used because we don’t want to remove oxide from the sides.
Cleaning

Prof. Milo Koretsky


Chemical Engineering Dept .

Particle Removal: SC-1


H2SO4 H2O Rinse H2O : HF H2O Rinse

• Particles from processing H2O2


125oC
Room Temp (10 : 1)
Room Temp

steps, machinery or handling


can contaminate wafers. H2O / NH4OH /H2O2
(5:1:1)
H2O Rinse
Room Temp
H2O / HCl /H2O2
(6:1:1)
80oC 80oC

• These particles are removed


by the SC-1 clean. H2O Rinse
Room Temp
H2O : HF
(100 : 1)
H2O Rinse
Room Temp
Alcohol (IPA)
Dry
Room Temp Room Temp

• The name of the solution used in this clean is Standard Clean -1


or SC-1 solution. Also called APM or RCA-1.
• The cleaning solution is a mixture of five parts de-ionized
water(H2O*), one part ammonium hydroxide (NH4OH ) and one
part hydrogen peroxide(H2O2 ).

Cleaning

Prof. Milo Koretsky


Chemical Engineering Dept .
SC-1 Clean
• Recipe: H2O / NH4OH / H2O2 80oC
(5:1:1)

• Removes: Particulates
• Action:
This works in two ways
1) By repulsion of like charges
• Both the particle and the wafer get negatively charged when
dipped in the solution. The particle is repelled from the surface.
Negatively
- - -
charged particle
- -
Negatively moves away
charged - - - - - - - - -- - - - - - - - -
surface Cleaning

Prof. Milo Koretsky


Chemical Engineering Dept .

SC-1 Clean - Electrochemistry!


Reduction Half reaction E0
O 3 + 2H+ + 2e - ¤ O 2 + H2 2.07
Reduced
Prefers

H 2O2 + 2H+ + 2e - ¤ 2H 2O 1.77


Form

Cu 2+ + 2e - ¤ Cu 0.34
3+ -
Fe + 3e ¤ Fe - 0.17
2+ -
Ni + 2e ¤ Ni - 0.25
3+ -
Cr + 3e ¤ Cr - 0.71
Oxidized

SiO2 + 4H+ + 2e- ¤ Si + 2H 2O - 0.84


Prefers

Form

Mn2+ + 2e- ¤ Mn -1.05


Al3+ + 3e - ¤ Al -1.66
Cleaning

Prof. Milo Koretsky


Chemical Engineering Dept .
SC-1 Clean
2) By chemical action
i) Hydrogen peroxide gives its extra oxygen to the silicon
substrate and makes a thin oxide film;
Si( s ) + 2 H2O2( l ) -> SiO2( s ) + 2 H2O( l ).
The oxide film lifts the particles.
ii) Ammonium Hydroxide etches the oxide and loosens the
particles; 2NH4OH( l ) + SiO2( s ) -> (NH4)2SiO3( l ) + H2O( l )
iii) The loose particles are removed by shaking.
Particle

Substrate

(i) ( ii ) ( iii ) Cleaning

Prof. Milo Koretsky


Chemical Engineering Dept .

Surface Metal Removal: SC-2


H2SO4 H2O Rinse H2O : HF H2O Rinse

• Surface metal contaminants H2O2


125oC
Room Temp (10 : 1)
Room Temp

are first oxidized


H2O / NH4OH /H2O2 H2O Rinse H2O / HCl /H2O2
• They are then removed by (5:1:1)
80oC
Room Temp (6:1:1)
80oC

reaction with hydrochloric


acid. H2O Rinse
Room Temp
H2O : HF
(100 : 1)
H2O Rinse
Room Temp
Alcohol (IPA)
Dry
Room Temp Room Temp

• The name of the solution used in this clean is Standard Clean -2


or SC-2 solution. Also called HPM or RCA-2.
• The cleaning solution is a mixture of six parts de-ionized
water(H2O*), one part hydrochloric acid (HCl) and one part
hydrogen peroxide(H2O2 ).

Cleaning

Prof. Milo Koretsky


Chemical Engineering Dept .
SC-2 Clean - Electrochemistry!
Reduction Half reaction E0
Reduced O 3 + 2H+ + 2e - ¤ O 2 + H2 2.07
Prefers

+ -
H 2O2 + 2H + 2e ¤ 2H 2O 1.77
Form

2+ -
Cu + 2e ¤ Cu 0.34
Fe 3+ + 3e - ¤ Fe - 0.17
2+ -
Ni + 2e ¤ Ni - 0.25
3+ -
Cr + 3e ¤ Cr - 0.71
Oxidized

SiO2 + 4H+ + 2e- ¤ Si + 2H 2O - 0.84


Prefers

Form

Mn2+ + 2e- ¤ Mn -1.05


Al3+ + 3e - ¤ Al -1.66
Cleaning

Prof. Milo Koretsky


Chemical Engineering Dept .

SC-2 Clean
• Recipe: H2O / HCl / H2O2 80oC
(6:1:1)

• Removes: Surface metal ions


• Action:
• hydrochloric acid reacts with the ions and removes them.

Cl - Chloride ions from HCl react with


aluminum ion and carry it away
Cl - -
Al +++ Cl

Cleaning

Prof. Milo Koretsky †


Chemical Engineering Dept .
Vapor Dry
H2SO4 H2O Rinse H2O : HF H2O Rinse
H2O2 Room Temp (10 : 1)

• Recipe: Isopropyl Alcohol (IPA)


125oC Room Temp

Removes: water from wafers H2O / NH4OH /H2O2 H2O Rinse H2O / HCl /H2O2
(5:1:1) Room Temp (6:1:1)

• Action: 80oC 80oC

• Alcohol vapors displace H2O Rinse


Room Temp
H2O : HF
(100 : 1)
H2O Rinse
Room Temp
Alcohol (IPA)
Dry
water from surface Room Temp Room Temp

•The alcohol evaporates more easily than water. It leaves a dry surface

Drop of
water

IPA Vapors IPA displaces water IPA evaporates


Cleaning

Prof. Milo Koretsky


Chemical Engineering Dept .

3. Gettering

Metals:
Traps on back
or in bulk

Alkali ions:
Dielectric layer
on topside SiO2 Precipitates

Cleaning
Damage induced
Prof. Milo Koretsky
Chemical Engineering Dept .