CN4223R Microelectronics Thin Film

FLEXIBILITY FOCUS FUTURE CLEANING

TECHNOLOGY
(SURFACE PREPARATION
PRIOR TO THIN FILM DEPOSITION)
your
next-generation
foundry
Associate Professor (Adjunct) Simon Chooi

Department of Chemical & Biomolecular Engineering

National University of Singapore

Text: ULSI Technology page 60-88, read selectively

 “Overview” In CN4223R

Metal & Metal alloy films

Physical Vapour Deposition Metal barrier films

(Sputtering)
Film Deposition in Vacuum
Dielectric films
(Vacuum Technology)
Polycrystalline silicon films
Chemical Vapour Deposition
Metal films

Cleaning Technology High k metallic films

Spin-on-glass (SOG)
Spin Coating
Film Deposition under Spin-on dielectrics (SOD)
Atmospheric Conditions

Electrodeposition Copper

CN4223R A/Prof Simon Chooi

 Why Cleaning Technology?
 Importance of a clean wafer surface before thin film deposition
Device performance, reliability and product yield are critically affected by the presence of chemical contaminants and
particles on the wafer surface

 Types of contamination
Particles, metallics (metals), organic and native oxide

CN4223R A/Prof Simon Chooi

 Wafer Cleaning

• Requirements for wafer cleaning:

(1) Effective removal of all types of contaminants from wafer surface without damaging or significantly
altering the wafer surface
(2) Minimal etching or damaging the underlying layer or substrate
(3) Use of contamination free and volatile chemicals
(4) Relatively safe, simple and economical for process application
(5) Ecologically acceptable and free of toxic waste product

• Three methods of cleaning: Wet Chemicals

Dry Physical
Vapour phase

• Wet chemical cleaning technology:

- Immersion (wet benches)
- Centrifugal spraying (spray processors)
- Single wafer spin etchers
- Megasonic processing
- Brush scrubbing
Dry physical cleaning, using cryogenic aerosol stream
of Frozen argon and nitrogen gas (FSI ANTARES)

CN4223R A/Prof Simon Chooi

Wet Cleaning: Immersion Systems (Wet Benches)

FSI Magellan immersion wet bench

CN4223R A/Prof Simon Chooi

 Wet Cleaning: Spray Processors

Spraying chemical across the wafers creates a physical force that acts to remove contamination

Semitool FSI Zeta/Mercury

On-axis spray processor Off-axis spray processor

CN4223R A/Prof Simon Chooi

Wet Cleaning: Single Wafer Spin Etchers

CN4223R A/Prof Simon Chooi

 Removal of Particles From Silicon Surface

 Particle adhesion due to several mechanisms:

(1) Forces due to static charge
(2) Van der Waals forces
(3) Chemical bonding between particle and surface

 Particle removal mechanisms:

(1) Dissolution
(2) Oxidizing degradation followed by dissolution
(3) Liftoff by slight etching of the wafer surface or substrate
(4) Electric repulsion between particles and wafer surface

CN4223R A/Prof Simon Chooi

 Removal of Particles From Silicon Surface
 Particle removal typically achieved using SC-1 (NH4OH, H2O2, water); ratio from 1:1:5 to 1:1:200 at 70C
Mechanism comprises
(i) oxidation of organics
(ii) oxidation of Si under particle and simultaneous etching of the oxidised Si

Complex reactions summarised to the following:

Dissociation of hydrogen peroxide: H2O2  H+ + HO2-
Oxidation of silicon: Si + 2HO2-  2 OH- + SiO2
Dissolution of silicon oxide: SiO2 + OH-  HSiO3-

NH4OH etches the silicon: Si + 6OH-  SiO32- + 3H2O

 Effect of SC-1 on surface roughness

•

• Ratio

1:1:5 0.5:1:1

• Temperature of bath
• Cleaning duration
CN4223R A/Prof Simon Chooi
Removal of Particles: Megasonic Cleaning

CN4223R A/Prof Simon Chooi

 Metal Contamination & Removal From Silicon Surface
 Source of metal contamination: chemical solution, ion implantation or etching process

 Two mechanisms of metal impurities onto silicon surface:

(1) Direct binding by the charge exchange between a metallic
ion and hydrogen atom from Si-H

Not easy to remove

(2) Entrapment into oxide layer during formation

Removed by etching the oxide

▪ Removal using SC-2 (Standard Clean 2 or also known as HPM (Hydrochloric-Peroxide mixture):
HCl, H2O2, water, typically ratio of 1:1:6

CN4223R A/Prof Simon Chooi

 Organic Contamination and Removal
 Source of organic contamination: organic vapour in wafer fab ambient, storage containers, photoresist residue

 Organic contamination typically removed by:

(1) Dry ashing (oxygen radicals)
(2) Sulfuric peroxide mixture (SPM) – H2SO4 and H2O2 in the ratio between 3:1 to 10:1 and temperatures between
110C and 140C
(3) Ozone-injected deionized water

 Removal mechanism: Oxidation followed by dissolution

CN4223R A/Prof Simon Chooi

 Native Oxide on Silicon Surface
 Nature of native oxide: oxidation of silicon to silicon oxide, usually about 10 to 20Å

Native oxide growth in air

 Consequence of native oxide: Interference to thin film growth

(eg metal silicide formation)

 Removal: Native oxide can be removed by hydrofluoric acid (HF):

HF + SiO2  SiF4 + H2O or SiF6 + H2O + H2

Complete oxide dissolution:

original hydrophilic surface  hydrophobic surfae

CN4223R A/Prof Simon Chooi

 HF-Last Process for Silicon Surface
 The contact angle of a droplet of deionozed water on the silicon surface is usually used to indicate the chemical
condition of the surface

 Low contact angle (hydrophilic surface)

(native oxide)

 High contact angle (hydrophobic surface)

(no native oxide, HF-last)

https://www.youtube.com/watch?v=MPu3C1RgUf4 HF-last: Hydrogen termination on silicon

CN4223R A/Prof Simon Chooi
 Conventional Cleaning Sequence for Silicon Surface

SPM: H2SO4/H2O2 (4:1) 120-150C, remove organics

DI water rinse Room temperature, remove SPM

Dilute HF or DHF (100:1 H2O:HF) Room temperature, remove native silicon oxide

DI water rinse Room temperature, remove HF

SC-1: NH4OH/H2O2/H2O (1:1:5) 70C, remove particles

DI water rinse Room temperature, remove SC-1

SC-2: HCl/H2O2/H2O (1:1:6) 80C, remove metals

DI water rinse Room temperature, remove SC-2

Dilute HF or DHF (100:1 H2O:HF) Room temperature, remove native silicon oxide
HF-last cleaning

DI water rinse Room temperature, remove HF

CN4223R A/Prof Simon Chooi
Other Chemicals For Wet Cleaning

CN4223R A/Prof Simon Chooi