Chapter 5

Contamination Control
半導體製程
材料科學與工程研究所
張翼 教授
Figure 5.1 Relative size of one micron.

 Major contaminants:
1. Particles
2. Metallic ions
3. Chemicals
4. Bacteria
 Bacteria: Need const.
running water to prevent
bacterias
Figure 5.2 Relative size of contamination. (Hybrid
Microcircuit Technology Handbook)
Figure 5.3 Relative size of airborne particles and wafer
dimensions.

 As lines get smaller,

particle control becomes
more important.
 Killer defects: particles in
critical location
Contamination caused problems:

Device processing yield

Device performance
Device reliability
Contamination sources

1. Air
2. The production facility
3. Clean room personnel
4. Process water
5. Process chemicals
6. Process gases
7. Static charge
Figure 5.4 Example resist stripper trace metal contents
(EKC Technology—830 Photoresist stripper)
Process chemicals and process
water can be contaminated
with trace chemicals from wafer
process.
 MOS Grade = Low
sodium grade (sodium is
the most prevalent
mobile ionic contaminant)
 MICs: Mobile ion
contaminants
 Metals in an ionic form
can cause electrical
failure even after final
test since they are
movable.
 Exist in most chemical
 Need to be < 1010 atoms/
㎝2
Figure 5.5 Relative size of airborne particulates (microns).
Figure 5.6 Air cleanliness classes
standard 209E.

•regular air in city: 5M /ft3

Figure 5.7 Typical class numbers for various environments.

 Clean room design

strategies:
1. Clear air station
2. Tunnel design
3. Total clean room
4. Mini environments
Figure 5.8 Hepa filter.

 Clean room starts with

space program: NASA, a
single speck can cause
satellite to fail.
 Fragile fiber with small
holes in accordion design
(手風琴)
 Air pass with large volume
and low velocity (not to
cause air currents)
 air flow → 90 - 100 ft/min
Figure 5.9 Cross section of VLF hood.

 HEPA (High Efficiency

Particulate Attenuation)
~ 99.99+ efficiency

 (work station) vertical

laminar flow

 ＊important: (1) HEPA (2)

positive pressure
Figure 5.10 Cross section of a VLF-fume-exhaust hood.

Safety + No contamination

 Wet Chemical Process Hood

wafer storage
Figure 5.11 Cross section of clean-room tunnel.
Divide fabrication area into
separate tunnels or bays

 To prevent contamination
from too many people
working in the same room:
use Tunnel/Bay concept

Fewer people work in one bay

Figure 5.12 Cross section of laminar flow clean room.
(Courtesy of Semiconductor International.)

 Recovery: the time

required for the filters to
return the area to
acceptable condition
after a shift start,
personnel break or other
disturbance. Class 1:6
seconds
Figure 5.12

air return

open work station with

perforations
Figure 5.13 Wafer transfer microenvironment.

 Cost billion USD to build

clean room. Use micro /
mini environments to
reduce cost → isolate the
wafer in as small an
environment as possible.
Figure 5.13

pressure air / N2
Figure 5.14 Minienvironment system elements.

 (WIT): wafer isolation

technology

 low construction and

operating cost

 with > 8’wafer → too

heavy to carrier, too
expensive to drop
Figure 5.14

 Mechanical interface
Figure 5.15 Fab area with growing area, air showers, and
service aisles.

 Temperature: 72℉±2℉
(stable chemical reaction)
 Humidity: important for
polymer (too wet,
polymer is not sticky)
(too dry,static charge)
 relative humidity: 15 ~
50%
 smog control: ozone
filtered by carbon
Figure 5.15

Service bay

Positive air pressure

static control

Double door

Shoe glove cleansers

Adhesive flow mats
Figure 5.16 Triboelectric series. (Hybrid Circuit Technology
Handbook, Noyes Publications)

 Static charge formed by

triboelectric charge
(formed when two
materials initially in
contact are separated)

 One surface loses e-

 One surface gains e-
Figure 5.16

 loses e-
Figure 5.16

 gains e-
Figure 5.16

 (1) High density circuits with submicron feature size

vulnerable to smaller particles attracted by static charge.
Static charges build up on wafer storage boxes, work
surface, equipments. Can be as high as 50,000 volt to
attract aerosols from air or personnel garments. Very
difficult to remove.
 (2)ESD (Electric Static Charge) can destroy devices. Need
to package devices with antistatic materials
Figure 5.17 Static-charge reduction techniques.

 Preventions:
(1) Use antistatic materials in
garments and storage boxes.
(2) Use antistatic solution
(apply to the wall),but not in critical
area to prevent contamination from the
solution
(3) Grounded static discharge straps.
(4) Ionizer (underneath the Hepa or
close to the Nitrogen blow gun) to
neutralize the charge built up in the
filtered air.
Other static change examples:

(1) Photomask and rectile damage. ESD discharge can

vaporize and destroy the chrome pattern.
(2)ESD discharge between package material (PFA) for wafer
and equipment produce EM interference with machine
operation.
Static Charge Prevention

(1) Use antistatic materials in garments and storage boxes.

(2) Use antistatic solution (apply to the wall)
(3) Grounded static discharge straps.
(4) Ionizer (underneath the Hepa) to neutralize the charge
built up in the filtered air.
Figure 5.18 Activity-caused increase in particles.
over background=1
(Hybrid Microcircuit Technology Handbook,Noyes
Publications)

 Human: biggest source

of contamination
 After showering and
sitting, gives off 100,000
~ 1,000,000 particles/min
 Hair spray cosmetics,
smoking, pencil must be
prevented.

 Gowning from top to

bottom. Undress from
bottom to top.
Figure 5.19 Resistivity of wafer versus concentration of
dissolved solids.

A Fab uses millions of gallons

of water per day.
Water contaminants if nor
processed:
1.Dissolved minerals
2.Particulates
3.Bacteria
4.Organics
5.Dissolved oxygen
6.Silica
D.I water 18,000,000 Ohms-
cm at 25 degree C
Process chemicals

 Contaminants: metallic; particulates; chemicals

 Grades:
commercial ~ too dirty for IC
reagent ~ too dirty for IC
electronic ~ cleanliness depends on manufacturer
semiconductor ~ cleanliness depends on manufacturer
 usually MIC level 1 ppm, some supplier provide 1 ppb
 particle filtering level 0 - 2μm or lower.
 Usually purchase bulk quantities
(prevent container contamination)
Process for Cleaner Chemicals

 BCDS (Bulk Chemical Distribution Systems) →cleaner

chemical / lower cost
 Point of use (POU), mix chemical at process vessel.
 Point of use chemical generation (POUCG)
Chemical made at process station, to reduce contamination
and cost. (such as NH4OH,HF, H2O2)
Gas Quality

1. Purity
2. Water vapor contents
3. Particulates
4. Metallic ions
Process with gas reactions

Oxidation
Reactive ion etch
Sputtering
Plasma etch
CVD
Contamination Control

 Contamination may change the chemical reaction

 Gas Purity 99.99 ~ 99.999999%(Highest purity, with six
9’s)
 Water vapor is limited to 3 - 5 ppm, or it can oxide the Si
surface
 Gas filtered (Particulates ~ 0.2μm)
 MIC < ppm
Water Requirements
 Regular wafer contains:
1. Dissolved minerals ~ removed by ion exchange system.
2. Particulates ~ removed by sand, earth, membrane
filtration.
3. Bacteria ~ removed by sterilizer
4. Organics ~ removed by carbon bed filtration.
5. Dissolved oxygen ~ removed by decarbonator & vacuum
degasifier
6. Silica
 Monitor water resistivity in several points in fabrication
area.
 Standard 18,000,000Ω-㎝ at 25℃ (18 megohm 18mΩ)
water
Clean Room Materials and Supplies:

Notebook
Tools
Pencils
Storage boxes
Cartwheels

Need special materials, which don’t generate particles

Clean Room Maintenance:

Cleaner
Applicator
Wiper
Vacuum cleaner with Hepa filter
all need special materials
Wafer Surface Cleaning

 Wafer surface contamination:

1. Particulates
2. Organic residues
3. Inorganic residues
4. Unwanted oxide layers

 Wafer surface roughness requires 0.15 nm (nmRMS) root

mean square of vertical surface roughness.
 In 2010 (nmRMS)<0.1nm
 Excess surface roughness effect device performance and
layer unifromaity
Surface Contamination

 Surface contaminant type

1.Particulates
2.Organic residues
3.Inorganic residues
4.Unwanted oxides
 Gate oxide need <0.02 defects/㎝2 when tested at 5MV/㎝ 30
secs
 Zn, Na, Fe, Ni, Ca<2.5*109 atoms/㎝2
 Al,Ca < 5*109 atoms/㎝2
 FEOL: Front End of the Line (from active layer)
 BEOL: Back End of the Line
Figure 5.20 DRAM water specs. (Semiconductor
International, July 1994, p. 178)
 Figure 5.21 Typical deionized water system.

Water stored is blanked with nitrogen to

prevent the
Absorption of carbon dioxide.Carbon dioxide
interfere with resistivity may cause wrong
reading
Figure 5.22 Sources of particulate contamination. This
analysis, shown at SEMI Forecast by Dr. C. Rinn Cleavelin,
Texas Instruments, revealed equipment-generated particles
as the top enemy in 1985.

 PWP: Particles per Wafer

Pass
 Equipment need material
and design selection and
assembled in a clean
room environment.
Figure 5.23 Typical FEOL cleaning process steps.

Standard clean
 Particulate removal

Small particulate held to surface by :

1.van der Waals force ( strong inter-atomic attraction between the

electrons of one atom and nucleus of another)
2. Capillary force (Occurred when there’s liquid bridge between
particle and the Surface)

Zeta Potential: arises from a charge zone around particles that is

Balanced by opposite charge zone in the cleaning liquid

Van der Waals force can be minimized by Zeta potential

The charge in the liquid varies with cleaning liquid speed, PH of the
solution, concentration of the electrolytes in the solution, additives
in the solution, such as surfactant. These conditions create a large number of
charge that has same polarity of the wafer and create repulsive force to
keep the particle in the solution and off the wafer surface

Surfactant and mechanical assist tool (such as megasonics)

are used to dislodge the particle attached to the surface by capillary force
Figure 5.24 Capillary force from film.

Occurred when there’s liquid

bridge between particle and
the surface

Surfactant and mechanical

assist are used to dislodge
the particle
 Most commonly used cleaning process

Nitrogen blow off:

1. Spray of filtered high pressure nitrogen
2. Ionizer strip static charges from the nitrogen
stream and neutralize the wafer surface
Figure 5.25 Mechanical scrubber.

Wafer hold by a rotating vacuum

Chuck

Brush and wafer rotation create high

energy cleaning action

Liquid forced between the space with

high velocity adds to cleaning

Dilute NH4OH is added to the cleaning

solution to control zeta potential
RCA clean

SC1-
H2O,H2O2,NH4OH ratio from 5:1:1-7:2:1
Used at 75-85 degree C
Oxide keeps forming and dissolving
Removes organic residues and sets up a condition for desorption
of trace metal from the surface

SC2-
H2O,H2O2, HCl ratio from 6:1:1 to 8:2:1
Used at 75-85 degree C
Removes alkali ions, hydroxides and complex residue metal

If oxide free surface is needed, HF etch is added before or after RCA clean

Metal ions are not dissolved in most cleaning solution, need to add chelating
agent (ethylenediamine-tetra-acetic acid)

Dilute solutions, SC1 (1:1:50), SC2 (1:1:60) are usually used with same
effectiveness and with less roughness on the surface.
 Photomask Cleaning

High pressure water spray (2000-4000 psi)

Add small amount of surfactant as destatic

agent
Organic residue removal

Use TCE, Aceton, Alcohol

Problems:
Solvent cleaning is difficult to dry and contains
contaminants
Chemical Cleaning

H2SO4 + Oxidant { (H2O2, [(NH4)2S2O3],HNO3,

OZONE)}

H2SO4 is effective cleaner for inorganic residues

and particles from 90o C to 120oC

Oxidants are added to remove carbon residues by

converting C to CO2 which leaves as vapor
 C+O2=CO2 (gas)
Chemical Cleaning (CONTINUE)

H2SO4 + 30% H2O2 (by volume)

(Carro’s acid or Piranha acid)

Used for all stages of processing and

photoresist stripper
Exothermic reaction, T=110-130 degree C
Need to add H2O2 to maintain the cleaning rate
(As time proceeds, temperature falls and reaction
rate falls)
 Ozone addition

Ozone can be used in the sulfuric acid

instead of oxidant additive

Ozone can also be added to D.I. Water (1-2ppm)

to provide a cleaning solution for light
organic contaminants (for 10 minutes at room
temperature)
 Oxide layer removal

Thin oxide (100-200Å ) formed in air or in the heated

chemical bath with the presence of oxygen

Thin oxide is an insulating layer which prevents

Electrical contact between Si and metal, also prevents
silicon surface from chemical processes

Hydrascopic-silicon surfaces with oxide

Hydrophobic-silicon surfaces that are oxide free
 Oxide layer removal (continue)

Before Oxidation process Si surface is cleaned in 49%

HF, which etches oxide but not Si

In later process, oxides in patterned holes are etched

in water and HF solution (strength from 100:1 to 10:1)
Strength is chosen that solution will etch oxide in the
Hole, but not the silicon (typical dilutions from
1:50-1:100)

Pregate cleaning uses HF as the last chemical step

(HF-last)- surface is hydrophobic and low metal
contamination
Figure 5.26 RCA clean formulas.

Developed by
RCA engineer
Werner Kern
in mid 1960s
to remove
Organic and
inorganic residues
from silicon surface
Figure 5.27 Experimental room temperature cleaning
process.

Combine Water,
HF + Ozone in
Megasonic for
cleaning
 Spray cleaning

Standard cleaning process using immersion in chemical

baths performed in wet bench
Immersion process is expensive (needs a lot of solution),
causes redeposition of contaminants on the surface, and
smaller and deeper patterns are difficult to clean

Spray cleaning advantages:

Chemical costs are down, cleaning efficiency is low,
less recontamination due to spray
Pressured spray assists in cleaning small patterns
Rinsing after cleaning in the same machine without
separate station
Figure 5.28 CO2 “SNOW” cleaning (Courtesy of Walter
Kern).

High pressure CO2 is directed

at the surface from the nozzle

Pressure drop causing rapid

cooling and forms CO2 particles
and snow

Impinging particles dislodge the

surface particles and flow carry
them away
Can also use argon:
Argon aerosol is large and
heavy can dislodge the particle
when directed to the wafer
under pressure

Nitrogen/argon can also be used

for this technique:
(cryokinetic)
 Water Rinse

Wet cleaning is followed by rinse in D.I. Water

Rinsing functions:
Removing cleaning chemicals
Stop oxide etch

Future direction:
Higher rinse efficiency, from 30 gal/sq.in. of Si to
2 gal/sq.in. of Si in 2012
 Dry cleaning

Vapor or gas phase cleaning

(E.g. HF/water mixtures)

Plasma etch

UV ozone cleaning: oxidize and photo-dissociate

contaminants from the wafer surface
Figure 5.29-(1)
Rinse systems: (a) single overflow

D.I.water from bottom

flow through around the
wafer, exitiy into over
a dam into drain system

Nitrogen bubbles up
through the water, aids th
mixing of the chem-
ical with the water on
wafer surface (bubbler)
Figure 5.29-(2)
Rinse systems: (b) three-stage overflow
Figure 5.30 Parallel down flow rinsing (Courtesy of Walter
Kern).

Water brought into the system from

outside the rinser and flow down
through the wafer

Rinse usually take 5 minutes with water

flow rate equivalent to 5 times the
volume of the rinser per minutes
(5V/min)

Rinse time can be determined by

measuring the resistivity of the water
(water resistivity meter is used, usually
exiting water is 15-18 megohm)
Figure 5.31 Spray-dump rinser.

Overflow rinser with spray capability

Spray rinsing

Flow water removes water soluble chemicals and

carries the chemicals away

Faster flow rate will speed up the rinsing process

Spray rinsing removes the chemical with a physical

force from momentum and has a faster rinse rate

Advantages:
Faster rinse rate, more efficient rinsing
Use less water
Disadvantage:
Carbon dioxide from air get trapped in the spray
and form charged particles and resistivity meter reads
them as contaminants
 Figure 5.32 Ultrasonic/megasonic wafer cleaning/etching
bath.

Ultrasonic:20,000-50,000 Hz,waves passes liqyid causing microscopic bubbles to form and collaps
rapidly creating scrubbing action that dislodge the particles (cavitaion)

Megasonic:850KHz, small particles held on the wafer surface due to slow moving boundary layer
on the wafer surface, leaving the particle unexposed to the cleaning chemicals,megasonic energy r
the stagnant layer on the wafer surface, exposing particles to the cleaning solutions,also,acoustic s
fosters an increase in the velocity of the rinse and cleaning solutions past the wafer surface, increa
cleaning efficiency
Figure 5.33-(1)
Spin rinse dryer styles. (a) Multiboat

Rinse the wafer with

Water from central
pipe, than rotate with
high speed with hot
nitrogen from the
center pipe.The rotation
throw water off the wafer
And the hot nitrogen
remove the water droplet
Drying Technique
 Spin Rinse dryers
 Isopropyl Alcohol (IPA) Vapor dry
 Surface Tension/ Marangoni Drying
Figure 5.33-(2)
Spin rinse dryer styles. (b) single boat axial

Axial dryer:water
and nitrogen come
through the side,
rinse and drying
take place while
spinning
Figure 5.34 Vapor dry (Courtesy of Walter Kern).

Alcohol drying:
Heated reserve of
Liquid IPA with vapor
Cloud above it. When
Wafer with residual
Water on surface is
Suspended in the
Vapor zone, the IPA
Replaces the water,
Chilled coils around
the vapor zone con-
dense the water vapor
Out of the IPA, leaving
The surface water free
Figure 5.35 SIA Roadmap Projections (Micro October 1998
p. 54).
Surface Tension/Marangoni
Drying
 Surface tension draws the water away
from the surface, leaving it dry.
 IPA and nitrogen are directed at wafer
water level interface.
 IPA/Nitrogen flow created a surface
tension gradient causing a water flow
from surface into the water. This internal
flow further enhances the removal of
water from the wafer.