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EE6601 MicroFabrication Technology

NTU-EEE-Tse MS

EE6601 MicroFabrication Technology

A/P Tse man Siu Tel : 6790-4843 Email : emstse@ntu.edu.sg

Photolithography Processing

Photolithography Technology Photoresist Technology

Advanced Lithography

Metrology Defect Inspection and Analytical Techniques

References:

1. The science and engineering of microelectronic fabrication, Stephen A. Campbell, Oxford, 2001

2. Semiconductor Lithography Principles, practice and materials, Wayne M. Moreau, Plenum Press

3. Silicon Processing for the VLSI Era Vol 4 Deep-submicron Process Technology, S Wolf, Lattice Press

4. Semiconductor Materials and Device Characterization, Dieter K. Schroder, Wiley Interscience

5. Semiconductor Manufacturing Technology, Michael Quirk and Julian Serda Prentice Hall

6. Handbook of Microlithography, Micromachining, and Microfabrication, Volume 1: Microlithography, Editor P. Rai - Choudhury, SPIE Optical Engineering Press, 1997

Photoresist Technology

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Photolithography and Photoresist Technology

Photolithography Process Basic concepts for photolithography, process overview, negative and positive lithography, critical dimension generations, light spectrum, resolution and process latitude, Eight basic steps of photolithography process.

Photolithography Technology Purpose of Lithography, Purpose of alignment and exposure, Properties of light for optical lithography, Critical aspects of optics, Resolution and its critical parameters, Photolithography equipment, Reticles and Photomasks, Alignment and Overlay

Photoresist Technology

Purpose of Photoresist, Components of Photoresist, Conventional g-line and i-line

photoresists, Deep UV resists, Metrics of Photoresist, Characterization of Working Windows

Advanced Lithography

Optical Resolution Enhancement Techniques(RET) for sub-wavelength lithography,

Top Surface Imaging, Immersion UV Lithography, Double Patterning Lithography,

Extreme UV Lithography, E-beam Lithography, X-Ray Lithography, Nano-Imprint Lithography

Photoresist Technology

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Photoresist Technology

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1.

Purpose of Photoresist

2.

Components of Photoresist

3.

Conventional g-line and i-line photoresists

4.

Deep UV resists

5.

Metrics of Photoresist

6.

Characterization of Working Windows

Photoresist Technology

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Wafer Fabrication Process Flow

Wafer fabrication (front-end)

Diffusion

Thin Films

Photo

Polish

Etch

Implant

Wafer start wafer
Wafer start
wafer

Unpatterned

Completed wafer

Implant Wafer start wafer Unpatterned Completed wafer Test/Sort Note: wafers flow from photo step into only
Implant Wafer start wafer Unpatterned Completed wafer Test/Sort Note: wafers flow from photo step into only

Test/Sort

Note: wafers flow from photo step into only two other areas: etch and ion implant

Photoresist Technology

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EE6601 MicroFabrication Technology NTU-EEE-Tse MS Wavelength (nm) Photoresist Technology 5

Wavelength (nm)

Photoresist Technology

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Excimer Laser Sources for

Semiconductor Photolithography

 

Pulse

CD

Material

Wavelength

(nm)

Max. Output

(mJ/pulse)

Frequency

(pulses/sec)

Length

(ns)

Resolution*

(m)

KrF 248 300 – 1500 500 25 0.25 ArF 193 175 – 300 400 15
KrF
248
300 – 1500
500
25
0.25
ArF
193
175 – 300
400
15
0.18
F
2
157
6
10
20
0.15

Move to 193 nm: optical materials have undesirable absorbance and are more sensitive to laser damage, move from quartz to CaF2 lenses

Note :

* CD Resolution without Resolution Enhancement Techniques (RETs)

Photoresist Technology

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Minimum linewidth and exposure wavelength

YEAR

Linewidth (nm)

Wavelength (nm)

Remarks

1986

1,200

436

Hg : g-line

1988

800

436/365

Hg: g-line/i-line

1991

500

365

Hg: i-line

1994

350

365/248

Hg: i-line/DUV

1997

250

248

KrF DUV

1999

180

248

KrF DUV +RETs

2001

130

248

KrF DUV + RETs

2003

90

248/193

KrF/ArF DUV +RETs

2005

65

193

ArF DUV+RETs

2007

45

193

ArF DUV IML

2010

32

193

ArF DUV IML, DPL

2014

22

193

ArF IML + DPL

Photoresist Technology

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Three Ways to Improve Resolution

Shorter wavelength (436 nm…365 nm …248nm …193 nm…13.5 nm)

Reduce 
Reduce 

R  k 1 Reduce k 1
R 
k 1
Reduce k 1

(NA)

Increase NA
Increase NA

Immersion with NA>1

Improved masks (CD control, Phase Shift masks)

Improved lenses (aberrations)

Better photoresists

Better process controls

Resolution Enhancement Techniques (RET) k 1 = 0.25 achievable

Better photoresists • Better process controls • Resolution Enhancement Techniques (RET) k 1 = 0.25 achievable

Photoresist Technology

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Improvement in Resolution means Depth of Focus becomes an issue

DOF  k Decrease as k 1 
DOF
 k
Decrease as
k 1 
Decrease as  
Decrease
as  

2 (NA)

2

Decrease as NA 
Decrease
as NA 

However, DOF is no longer an issue. Wafers are made PLANAR with chemical mechanical polishing (CMP), allowing the lithography systems to work with smaller DOF.

Photoresist Technology

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1. Purpose of Photoresist in Wafer Fab

To transfer the mask pattern to the photoresist on the top layer of the wafer surface

To protect the underlying material during subsequent

processing e.g. etch or ion implantation.

What is resist?

Viscous liquid which has a “solid” form when solvents are driven out

Spin coated on wafer surface to be patterned

Exposure of resist to energy/radiation leads to (photo) chemical reactions and changes the resist dissolution rate in the developer

• Remaining resist is “rugged” enough to protect (mask) underlying

substrate during subsequent processing (etch and implant)

Photoresist Technology

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Progressive Improvements in Photoresist

Better image definition (resolution).

Better adhesion to semiconductor wafer

surfaces.

Better uniformity characteristics.

Increased process latitude (less sensitivity

to process variations).

Photoresist Technology

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Types of Photoresists

Two Types of Photoresist

Positive Resist

Negative Resist

CD Capability

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Conventional g-line, i-line Resist (resolution > 0.5 µm)

Deep UV Resist (resolution < 0.5 µm)

Process Applications

Non-critical Layers (g-line, i-line resists)

Critical Layers (DUV resists)

Photoresist Technology

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Photolithography Process

Creating the Patterns in Semiconductor Chip Manufacture

Creating the Patterns in Semiconductor Chip Manufacture Positive Resist - Mask image is same as wafer

Positive Resist -Mask image is same as wafer image -Exposed resist softens and is soluble -Developer removes exposed resist

Photoresist Technology

Negative Resist -Wafer image is opposite of mask image -Exposed resist hardens and is insoluble -Developer removes unexposed resist

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Negative Versus Positive Resists

Negative Resist

Wafer image is opposite of mask image

Exposure causes the resist to cross-link and harden,

becoming insoluble in Xylene developer

Developer removes unexposed resist

Negative resist is uncommon today because of

limited resolution (negative DUV resist has poorer

performance than positive DUV resist)

Positive Resist

Mask image is same as wafer image

Exposed resist softens and is soluble in hydroxide

developer

Developer removes exposed resist

Photoresist Technology

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2. Components of Photoresist

Technology NTU-EEE-Tse MS 2. Components of Photoresist Photoresist Technology Solvent : gives resist its flow
Technology NTU-EEE-Tse MS 2. Components of Photoresist Photoresist Technology Solvent : gives resist its flow

Photoresist Technology

Solvent:

gives resist its flow characteristics

Resin: mix of polymers used as binder; gives resist mechanical and chemical properties

Sensitizers:

photosensitive component of

the resist material

Additives:

chemicals that control specific aspects of resist material

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Photoresist components

Main components for lithographic capability:

Polymer (resin) - not opaque at

- Chemical reactivity

- Etch resistance

Sensitizer - Photo Active Compound/Group (PAC/PAG) at

Solvent

- Keeps photoresist in liquid state Allows spin coating of the photoresist

Solvent content determines viscosity and hence thickness!

Additives

Capability for further process:

Etch sensitivity/Implant blocking capability.

Photoresist Technology

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3. Conventional g-line and i-line photoresists

Types of Photoresist

Positive Optical Resist

Matrix (Novolac resin)

Sensitizer / dissolution inhibitor (PAC=diazoquinones)

Solvent (Propylene Glycol Methyl Ether Acetate (PGMEA), N-Methyl Pyrrolidene(NMP), n-butyl acetate, xylene, etc)

Developer: Hydroxides (TMAH, KOH, NaOH etc)

Negative Optical Resist

Cyclized synthetic rubber resin

Sensitizer(PAC=bisarylzide)

Solvent (aromatic solvent)

Developer: organic solvents

Photoresist Technology

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Negative Resist Cross-Linking

Areas exposed to light become crosslinked and resist the developer chemical.

UV
UV

Crosslinks

Unexposed areas

remain soluble to

developer chemical.

Photoresist Substrate Soluble
Photoresist
Substrate
Soluble
Oxide
Oxide

Unexposed

Exposed

Pre-exposure - photoresist

Post-exposure - photoresist

Post-develop - photoresist

Photoresist Technology

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Components of g-line & i-line positive Photoresist

Component

Typical Chemicals

Purpose

Remarks

Solvent

Propylene Glycol Methyl Ether Acetate (PGMEA)

gives resist its flow characteristics

Compatible to other components

Resin

Novolac resin

mix of polymers used as binder; gives resist

- Chemical Reactivity

- Transparent to g-line and i-line UV

mechanical and

- Reactive Ion Etch Resistance

chemical properties

-

Implant blocking capability

Sensitizers

DiazonapthoQuinone

Photo-Active Compound, PAC,

PAC acts as dissolution inhibition of resin, on absorption of UV

(DNQ),

photosensitive

light, PACs undergo chemical

component of the resist material

changes to increase the dissolution in alkaline developer

Additives

Surfactants, adhesion promoter, dyes

chemicals that control specific aspects of resist material

dyes can also be added into the photoresist composition to reduce scattered light from the reflection in the resist/substrate interface.

Photoresist Technology

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DNQ based positive g-line and i-line photoresist

The Novolac polymer solid (a phenol formaldehyde polymers) is an alkali-soluble resin. The developer solution, typically with a concentration of 0.2N to

0.26N or 2.36% to 2.38% of TMAH, used for

photolithography processing is a mild base, all Novolac-based positive photoresist would be dissolved in TMAH developer unless an inhibitor DNQ is added in the photoresist formulation.

The inhibitor is also called the photoactive compound, the PAC. The DNQ (diazonapthoquinone) inhibitor is sensitive to UV light and can be decomposed on absorption of UV light during exposure. A latent

photoresist pattern can thus be formed on exposure to

UV light through the photomask. The latent pattern in exposed areas of the photoresist film can be developed by dissolving the in TMAH developer solution. In the unexposed areas, the PAC molecules are intact, the resin dissolution in TMAH developer

solution is inhibited.

Photoresist Technology

The base resin is novolac a long chain polymer consisting of hydrocarbon rings with 2 methyl groups and 1 OH group attached.

polymer consisting of hydrocarbon rings with 2 methyl groups and 1 OH group attached. Novolac ~

Novolac ~ 20%

DNQ 1 – 10%
DNQ
1 – 10%

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DNQ based positive g-line and i-line photoresist

The Solvent propylene glycol methyl ether

acetate (PGMEA) gives the flow characteristics of the resist. It must be compatible with the Novolac polymer and the PAC. Its percentage content determines the viscosity of the resist and hence the resist film thickness on coating.

The solvent is removed during the spin coating,

soft bake and hardbake steps.

during the spin coating, soft bake and hardbake steps. PGMEA ~ 70% The additives are chemicals

PGMEA ~ 70%

The additives are chemicals that control specific aspects of resist material :

Surfactants, adhesion promoter, dyes,

Photoresist Technology

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Chemical reaction of DNQ based g-line and i-line resists

PAC

Wolf Re-arrangement Ketene
Wolf
Re-arrangement
Ketene

Dissolution inhibition chemistry.

One-step chemistry during exposure.

Light exposure breaks N2 bond in DNQ complex molecules, eventually transforming to carboxylic acid

The water in this reaction is obtained from humidity in the air and also the small amount of water present in the photoresist film. If the air is not humid enough, the remaining carbon bond will bond with the resin,

creating an insoluble material.

inden-3-carboxylic

Acid (dissolution enhancer)

The carboxylic acid is hydrophilic and the resulting N2 bubbles cause the exposed areas of the photoresist film to become porous. These two factors further enhance the dissolving capability of the TMAH developer solution on the UV exposed areas.

Photoresist Technology

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Chemical reaction of DNQ based g-line and i-line resists

Under UV exposure, the weakly bonded N2 free from the carbon ring, leaving a highly reactive carbon site.

One of the carbons moves outside the ring to stabilize the structure.

The oxygen atom is then covalently bonded to this external carbon atom. This

process is known as a Wolff rearrangement. The resultant molecule is called ketene

rearrangement . The resultant molecule is called ketene • The ketene immediately reacts with water molecule

The ketene immediately reacts with water molecule in the resist matrix to form

carboxylic acid. Carboxylic acid is soluble in base solution.

Dissolution rate in developer (hydroxide) changes

Resin composition

remark

Dissolution rate

Novolac only

Without sensitizer

150 Å/sec

Novolac with DNQ

With sensitizer

10-20 Å/sec

Novolac with Indene Carboxylic acid

After exposure

1000-2000 Å/sec

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PAC as Dissolution Inhibitor in Positive i-line Resist

UV
UV

Unexposed resist, containing PACs, remain crosslinked and

Resist exposed to light dissolves in the developer chemical.

insoluble to developer chemical.

Photoresist Substrate PAC Soluble
Photoresist
Substrate
PAC
Soluble
Oxide
Oxide

Exposed

Unexposed

Pre-exposure + photoresist

resist

Post-exposure + photoresist

Post-develop + photoresist

Photoresist Technology

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4. DUV photoresists

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- Chemically Amplified (CA) Resists

DNQ resist has large absorption

problem below 365 nm wavelength and not suitable for DUV technology

DUV resists rely on a new principle, so-called chemically amplified (CA) resists. A catalyst, the photo-acid generator (PAG), replaces the PAC.

Photoresist Technology

resists. A catalyst, the photo-acid generator (PAG), replaces the PAC. Photoresist Technology Absorbance of DNQ resist

Absorbance of DNQ resist

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Components of Chemically Amplified(CA) DUV Photoresists

Component

Typical Chemicals

Purpose

Remarks

Solvent

Propylene Glycol Methyl

gives resist its flow

Compatible to other

Ether Acetate (PGMEA)

characteristics

components

Resin

- tertiary-butoxycarbonyl

tertiary-butoxycarbonyl

Protection group makes it

parahydroxystyrene (tBOC-PHS) (248nm)

(tBOC) dissolution inhibitor protection group for 248CA resist; gives resist mechanical and chemical properties

insoluble in developer.

- phenolic copolymer

- cyclic olefin / maleic anhydride (COMA)

Transparent to 193nm DUV Etch resistance to plasma

polymers (193nm)

 

Sensitizers

triphenylsulfonium salt

Photo-Acid-Generator, PAG photosensitive component of the resist material

PAG acts as H+ catalyst for the de-protection of dissolution inhibitor of resin

Additives

Low MW additives to increase contrast,

chemicals that control specific aspects of resist

dyes can also be added into the photoresist composition

Surfactants, adhesion

material

to reduce scattered light from

promoter, dyes

the reflection in the resist/substrate interface.

Photoresist Technology

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DUV Emission Spectrum

KrF laser emission spectrum

100 80 60 40 20 0 Relative Intensity (%) Relative Intensity (%)
100
80
60
40
20
0
Relative Intensity (%)
Relative Intensity (%)

248 nm

Emission spectrum of high-intensity mercury lamp

120

100

80

60

40

20

0

i-line 365 nm g-line h-line 436 nm 405 nm DUV* 248 nm 200 300 400
i-line
365 nm
g-line
h-line
436 nm
405
nm
DUV*
248 nm
200
300
400
500
600

Photoresist Technology

Wavelength (nm)

* Intensity of mercury lamp is too low at 248 nm to be usable in DUV photolithography applications. Excimer lasers, such as shown on the left provide more energy for a given DUV wavelength.

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Chemical reaction of DUV CA resists

Chemically Amplified (CA) Resist for 248nm DUV Two-steps chemistry; dissolution inhibition. PAG triphenylsulfonium salt

Polymer/Resin -- PHS - polyhydroxystyrene

PAG – triphenylsulfonium salt Polymer/Resin -- PHS - polyhydroxystyrene Exposure PEB Photoresist Technology 28

Exposure

PAG – triphenylsulfonium salt Polymer/Resin -- PHS - polyhydroxystyrene Exposure PEB Photoresist Technology 28

PEB

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Chemically Amplified Resist

Exposure:

PAG irradiation forms acid at exposed areas.

PEB - Post Expose Bake:

Acid react with tBOC-PHS to form

soluble PHS + acid; chain reaction and amplification. Acid diffuses into the unexposed area.

Chain reaction stops at end of PEB process.

Resist base will neutralize the acid

Photoresist Technology

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neutralize the acid Photoresist Technology NTU-EEE-Tse MS Resulting line width  smaller than optically printed. 29

Resulting line width smaller than optically printed.

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Chemically Amplified “Solubility Switch” for 248 nm

Photoresists during PEB

“Solubility Switch” for 248 nm Photoresists during PEB • Chemical amplification: deprotection catalyzed by

• Chemical amplification:

deprotection catalyzed

by protons

• High aromatic content => High etch resistance

Before exposure, the phenol OH group of PHS is protected by the tBOC group. The base resin is insoluble in the developer solution such as tetramethylammonium hydroxide (TMAH) solution.

An triphenylsulfonium salt salt acts as a photo-acid generator and generates the acid

during the exposure.

The acid-catalyzed reaction induces chain reactions and deprotects tBOC during the PEB.

As a result, the phenol OH groups are generated in the exposed area and can be dissolved in the alkaline developer.

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Photoresist Technology

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Chemically Amplified (CA) DUV Resist

UV H + PAG H + H + PAG
UV
H +
PAG
H +
H +
PAG

Post-exposure + CA photoresist

Unexposed resist remains crosslinked and PAGs are

inactive.

Resist exposed to light

dissolves in the developer chemical.

Photoresist Substrate PAG PAG PAG PAG PAG
Photoresist
Substrate
PAG
PAG
PAG
PAG
PAG

Acid-catalyzed reaction (during

PEB)

Pre-exposure + CA photoresist

Oxide PAG PAG
Oxide
PAG
PAG

Post-develop + CA photoresist

Exposed

Unexposed

Unchanged

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Exposure Steps for Chemically- Amplified DUV Resist

1. Resin is phenolic copolymer with protecting group that

makes it insoluble in developer.

2. Photoacid generator (PAG) generates acid during exposure.

3. Acid generated in exposed resist areas serves as catalyst to

remove resin-protecting group (t-BOC) during post exposure

bake (PEB) step.

4. Exposed areas of resist without protecting group are soluble

in aqueous developer.

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5. Metrics of Photoresist

Photo activity

Resolution

Contrast

Sensitivity

Spectral Response

Bleaching Effect

Viscosity

Etch resistance

Thermal Stability

Polymer Requirement

Photoresist Technology

Adhesion Surface tension Storage and handling Standing waves Effect Anti reflective coating

Proximity effect

Environmental Effects - Contamination and

Particles

- T-Top Formation for DUV CA resist

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Photo Activity
Photo Activity

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Photospeeds of recording process

Process

ASA speed

(ergs/cm 2 ) -1

TV tube

10 4

B&W film 10 2

Xerox

1

Photoresists 10 -5

Dose

(ergs/cm 2 )

10 -4

10 -2

1

10 5

Resolution

(lines/mm)

5

50

100

5000

Source: Semiconductor Lithography Principles, practice and materials, Wayne M. Moreau, 1988 Plenum press, New York.

Photoresist is one of the most photo-sensitive chemical processes

Photoresist Technology

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Resolution = how fine a line the resist can reproduce from an aerial image

• Resolution of resist is determined by

Contrast, Thickness, Proximity effects

Swelling and contraction after development

Contrast = ability of resist to distinguish

between light and dark regions

Measured by exposing the resist of given

thickness to varying radiation dose and measuring dissolution rate

Photoresist Technology

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Resist Contrast

Poor Resist Contrast

Sloped walls

Swelling

Poor contrast

Resist Film
Resist
Film

Photoresist Technology

Good Resist Contrast

Sharp walls

No swelling

Good contrast

Resist Film
Resist
Film

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Contrast Curves

Positive

Resist

MicroFabrication Technology Contrast Curves Positive Resist Resist Contrast NTU-EEE-Tse MS Negative Resist • D100 =

Resist Contrast

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Negative

Resist

• D100 = exposure energy dose for complete resist removal

• D0= threshold exposure energy dose for resist removal

• Typical values

exposure energy dose for resist removal • Typical values under fixed developer conditions Resists with higher
exposure energy dose for resist removal • Typical values under fixed developer conditions Resists with higher

under fixed developer conditions

Resists with higher contrast result in better resolution because of more vertical resist profile

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Sensitivity and contrast for resists

Large sensitivity for CA DUV resists compared with conventional DQN resist:

20-40 mJcm -2 compared to 100 mJcm -2 typical for DNQs

Post-exposure bake very critical in DUV resist technology (chemical reaction occurs)

critical in DUV resist technology (chemical reaction occurs) Remaining photoresist against exposure dose Photoresist

Remaining photoresist against exposure dose

Photoresist Technology

Sensitivity : D 100 (D f )

Chemical Contrast --- slope of curve defined as :



1

log D

100

/ D

0

High high resolution/contrast

e.g.

DNQ g-line/i-line resist : = 2 - 3

DUV CA resist : = 5 - 10

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Critical Resist Modulation Transfer Function(CMTF)

MS Critical Resist Modulation Transfer Function(CMTF) In order to print lines : MTF e x p

In order to print lines : MTF exposure system ≥ CMTF resist

Sensitivity

Incident energy necessary to produce the photochemical reactions required for defining patterns

• Related to quantum yield

#of photon induced events

#of photonabsorbed



• Higher sensitivity required at shorter wavelength because of limited brightness of UV sources and optics efficiency

• Trade-off between exposure time and brightness

Photoresist Technology

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Effect of Sensitivity on Contrast

If I is intensity, α is the absorption coefficient T R is the resist thickness

The resist contrast can be shown to be

where β is a dimensional constant,

Spectral Response

Absorbance should not be too

high to prevent excessive absorption of UV light Upon exposure, resist must be more transparent

Photoresist Technology

absorption of UV light • Upon exposure, resist must be more transparent Photoresist Technology NTU-EEE-Tse MS

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absorption of UV light • Upon exposure, resist must be more transparent Photoresist Technology NTU-EEE-Tse MS

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Bleaching : the absorbance of most resists typically decreases on exposure. The actinic absorbance is defined as the difference between the unexposed and exposed absorbance.

the difference between the unexposed and exposed absorbance. DNQ resist • Bleaching can provide a more

DNQ resist

Bleaching can provide a more uniform exposure: the top layers of the resist become partially transparent when they are exposed, allowing a fuller exposure of the lower layers, thus achieving a vertical sidewall.

Photoresist Technology

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Resist Thickness (Å)

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Resist Viscocity

-- Effect of solvent and -- Spin Speed Curve

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Solvent keeps photoresist in liquid state Allows spin coating of the photoresist Solvent content determines viscosity and hence thickness!

Spin Speed Curve of IX300 (thick DNQ resist) for different viscosity 80000 70000 60000 50000
Spin Speed Curve of IX300 (thick DNQ resist) for different viscosity
80000
70000
60000
50000
110 cP
40000
70
cP
30000
20000
21
cP
10000
0 1000
2000
3000
4000
5000
6000
7000

Photoresist Technology

Spin Speed (RPM)

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Etch Resistance

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Etch Resistance = Once patterned, resist must be

able to stand up to etch chemistry (i.e. protect underlying material) and must be thermally stable

Other important resist parameters

• Thermal stability

• Adhesion (improved using HMDS-hexamethyldisilizane)

• Viscosity (% of solid content)

• Particulates and Metal content

• Flash point and TLV rating

• Process latitude, consistency, shelf-life

Photoresist Technology

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Thermal Stability of Photoresist and Enhancement of Thermal Stability with DUV Cure after Development

High temperature

bake are used to harden resist against further energetic processes such as ion

implantation and

plasma etching

• At sufficiently high enough temperature, the resist reflows changing the profile which can be troublesome for patterning some unique structures

Photoresist Technology

for patterning some unique structures Photoresist Technology Post Development DUV Cure improves Thermal Stability 44

Post Development DUV Cure improves Thermal Stability

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Technological Requirement for Photoresist Polymer backbones

Chemical Reactivity

UV Transparency not opaque

Reactive Ion Etch Resistance

Light should be absorbed by PAG, not binder polymer Avoid binder decomposition and outgassing Use light efficiently Allow light to penetrate to bottom of film for straight sidewalls » Absorbance < 2.0 µm-1, preferably < 1.0 µm-1

Photoresist Technology

Novolac based resist
Novolac based resist

45

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Technological Requirement for Photoresist Polymer backbones

The Need for Technology Shift

- Novalac is not transparent at < 300nm for DUV

- Parahydroxystyrene (PHS) based polymer backbones for 248nm DUV become opaque at 193nm DUV

- 2 New material classes suitable for 193nm DUV

- Acrylics

- cyclic olefin / maleic anhydride (COMA) polymers

Acrylics - cyclic olefin / maleic anhydride (COMA) polymers - Acrylics suffer from poor reactive ion

- Acrylics suffer from poor reactive ion etch resistance etch too fast

- Cyclic Olefins are the technological choice for 193nm

- perfluoropolymer for future 157nm

Photoresist Technology

46

EE6601 MicroFabrication Technology

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Absorption Spectra of Photoresist Polymer Backbones

Technology NTU-EEE-Tse MS Absorption Spectra of Photoresist Polymer Backbones Photoresist Technology 47

Photoresist Technology

47

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Design of a 193 nm Photoresist Polymer

NTU-EEE-Tse MS Design of a 193 nm Photoresist Polymer • Etch resistance from polycyclic groups in

• Etch resistance from polycyclic groups in backbone or side chains • Development by de-protection of tertiary alkyl ester

groups in backbone or side chains • Development by de -protection of tertiary alkyl ester Photoresist

Photoresist Technology

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EE6601 MicroFabrication Technology

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Design of a 193 nm CA Resist for Immersion Lithography

Chemically amplified resists (CARs) utilized at 193nm Immersion Lithography are

formulated with the following primary components;

- the polymer resin,

- casting solvents,

- Photo-Acid Generator (PAG), and

- base quencher.

- Additional components offer additional functionalities as needed in a given formulation.

Photo-Acid Generators The photoacid generators (or PAGs) react with photons, creating an acid which reacts with the polymer resin to deprotect the resin. The acid deprotection then allows the developer to dissolve the polymer chain.

Iodonium Salts

TBI-PFOS tert-butylphenyliodonium perfluorooctanesulfonate

Sulfonium Salts

TPS-PFBS triphenylsulfonium perfluorobutanesulfonate (or TPS-Nf triphenyl sulfonium nanoflate) TPS-Tf triphenylsulfonium trifluoro sulfonate (or triphenyl sulfonium triflate)

Photoresist Technology

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EE6601 MicroFabrication Technology

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Design of a 193 nm CA Resist for Immersion Lithography

Polymer Resins

The components of the polymer resin, generally a ter-polymer (3 components) or

tetra-polymer (4 components), are the backbone of the resist matrix. MMA methyl methacrylate TBMA t-butyl methacrylate MAA methacrylic acid

MAdMA 2-methyl-2-adamantanol methacrylate (for dry etch resistance)

GBLMA gamma butyrolactone

HadA MLMA mevalonic lactone methacrylate (for wetability and adhesion) COMA cycloolefine-maleic anhydride

BNC - t-butyl-5-norbornene-2-carboxylate

MA - maleic anhydride

HNC Hydroxyethyl-5-norbomene-2-carboxylate NC 5-norbornene-2-carboxylic acid VEMA vinyl ether-maleic anhydride

Photoresist Technology

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EE6601 MicroFabrication Technology

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Design of a 193 nm CA Resist for Immersion Lithography

MS Design of a 193 nm CA Resist for Immersion Lithography Structure of hybrid COMA/methacrylate copolymer

Structure of hybrid COMA/methacrylate copolymer (Clariant T2030)

Photoresist Technology

for Immersion Lithography Structure of hybrid COMA/methacrylate copolymer (Clariant T2030) Photoresist Technology 51

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EE6601 MicroFabrication Technology

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Design of a 193 nm CA Resist for Immersion Lithography

Casting Solvents

The casting solvent functions to dissolve the polymer resins and act as a carrier to uniformly

distribute the material during typical spin-coating processes, then predominantly evaporating away during the post-application bake (or PAB). PGMEA propylene glycol methyl ether acetate EL ethyl lactate MAK methyl amyl ketone PGME propylene glycol monomethyl ether

Base Quenchers The base quenchers limit the diffusion of the photogenerated acid and minimize blur. TBAH tetra butyl ammonium hydroxide TEA triethanolamine

TPA tripentylamine

Dissolution Inhibitor Lithocholate DI dissolution inhibitor

Developer The developer dissolves the deprotected polymer chains in the resist matrix. TMAH tetramethyl ammonium hydroxide (0.26N industry standard)

Photoresist Technology

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EE6601 MicroFabrication Technology

Adhesion and Surface tension

NTU-EEE-Tse MS

Wafer pre-clean

HMDS priming hexamethyldisilazane (HMDS) turns wafer surface from hydrophilic to hydrophobic for better photoresist adhesion. Si-dioxide + H2O + HMDS hexamethyldisiloxane + ammonia

+ H 2 O + HMDS  hexamethyldisiloxane + ammonia Storage and handling OH OH OH

Storage and handling

OH OH OH OH OH OH OH Si Si Si Si Si Si Si Silicon
OH
OH
OH
OH
OH
OH
OH
Si
Si
Si
Si
Si
Si
Si
Silicon wafer
+ NH 3
Si(CH 3 ) 3
Si(CH 3 ) 3 Si(CH 3 ) 3
Si(CH 3 ) 3 Si(CH 3 ) 3
Si(CH 3 ) 3
Si(CH 3 ) 3
O O
O O
O
O O
Si
Si
Si
Si
Si
Si
Si
Silicon wafer

Proper storage and handling of chemicals for repeatable photolithography results on wafers

Photoresist Technology

53

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Problems with Reflective wafer Surface

Photoresist Reflective Notching Due to Light Reflections from non-planarized surface

Mask

Edge

diffraction

Exposed

photoresist

Polysilicon

Photoresist Technology

UV exposure light

Unexposed photoresist Notched photoresist STI STI Substrate
Unexposed
photoresist
Notched photoresist
STI
STI
Substrate

Surface

reflection

54

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Standing Wave Effect in photoresist

NTU-EEE-Tse MS Standing Wave Effect in photoresist Standing wave effect causes modulation of the developed
NTU-EEE-Tse MS Standing Wave Effect in photoresist Standing wave effect causes modulation of the developed

Standing wave effect causes modulation of the developed photoresist edges

Photoresist Technology

55

EE6601 MicroFabrication Technology

Standing Waves Effect

Incident and Reflected Light Wave Interference in Photoresist

NTU-EEE-Tse MS

Incident wave Reflected wave Photoresist Film Substrate
Incident wave
Reflected wave
Photoresist
Film
Substrate

Reflected waves from reflective wafer surface cause standing

waves and hence non-uniform exposure along the thickness of the photoresist film and over surface topology.

Photoresist Technology

56

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Cause of Standing Wave Effect

Light reflectance inside the resist cause standing waves:

Standing Wave intensity

depends on:

Resist thickness Resist absorbance Light incident angle

The substrate film:

reflectivity, refractive index

Photoresist Technology

film: reflectivity, refractive index Photoresist Technology Period   Period 2n n : Resist refractive index
film: reflectivity, refractive index Photoresist Technology Period   Period 2n n : Resist refractive index

Period

Period

2n

n : Resist refractive index

57

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Variation of Exposure Dose due to Standing Wave Effect

The interference standing waves

may cause modulation in the exposure dose (total UV energy per unit area) for complete exposure of the photoresist to

vary with the photoresist film

thickness. The standing wave interference effect will also result in the variation in linewidth with changing photoresist thickness and such

phenomenon is sometimes

called the Swing Curve.

Swing Curve ---Variation of Exposure Dose modulation by g-line with resist film thickness

Dose modulation by g-line with resist film thickness Thickness fine tuning done by swing curve chart.

Thickness fine tuning done by swing curve chart. Preferred resist thickness:

an extreme point of the swing curve to reduce line-width variation.

Photoresist Technology

58

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Reduction of Standing Wave Effect

Reflected waves from wafer surface in particular those reflective layers such as metals causes reflective notching

and standing wave effect

Standing wave effect is a serious problem for fine line lithography when exposing on reflective surfaces

Suppression of reflected waves :

- Dyeing the photoresist to increase absorption on exposure and reduce reflected waves intensity - Post Exposure Bake (PEB)

- Antireflective coating (ARC) to reduce reflection wave

intensity --- Bottom ARC (BARC) prior to resist spinning - Top ARC (TARC) after resist spinning

Photoresist Technology

59

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Reduction of Swing Curve Amplitude

Increase absorption  by adding dye to the photoresist by adding dye to the photoresist

ARC – Anti Reflective Coating reduces reflection  reduces reflection wave amplitudes (R1 – top, R2 Anti Reflective Coating reduces reflection reduces reflection wave amplitudes (R1 top, R2 Bottom)

reduces reflection  reduces reflection wave amplitudes (R1 – top, R2 – Bottom) Photoresist Technology 60

Photoresist Technology

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Reduction of Reflection by Dyed Resist

The exposure modulation can be partially compensated using dyed version of the

photoresist by increasing the absorbance

of the exposed photoresist and hence reducing the reflected UV light intensity from the reflective substrate.

reflected UV light intensity from the reflective substrate. Reduction of Swing Curve amplitude with dyed

Reduction

of Swing

Curve

amplitude

with dyed

photoresist

Photoresist Technology

Absorpbance of S1813 photoresist

Photoresist Technology Absorpbance of S1813 photoresist Increased absorbance of S1813J2 dyed version photoresist on

Increased absorbance of S1813J2 dyed version photoresist on exposure

61

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Problem with Dyed Photoresist ---- Excessive Resist Absorption

1. The light intensity at the bottom of the resist is considerably less than that received at the top 2 . To achieve straight - wall images, the resist absorption <20 % ---- new resist materials for DUV 248nm and 193nm

Photoresist (after develop)

Photoresist (after develop)
resist materials for DUV 248nm and 193nm Photoresist (after develop) Substrate Photoresist Technology Sloping profile 62

Substrate

resist materials for DUV 248nm and 193nm Photoresist (after develop) Substrate Photoresist Technology Sloping profile 62

Photoresist Technology

Sloping profile

resist materials for DUV 248nm and 193nm Photoresist (after develop) Substrate Photoresist Technology Sloping profile 62
resist materials for DUV 248nm and 193nm Photoresist (after develop) Substrate Photoresist Technology Sloping profile 62

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Reduction of Standing Wave Effect by PEB

PAC PAC PAC PAC PAC PAC PAC PAC PAC PAC PAC PAC PAC PAC PAC
PAC
PAC
PAC
PAC
PAC
PAC
PAC
PAC
PAC
PAC
PAC
PAC
PAC
PAC
PAC
PAC
PAC
PAC
PAC
PAC
PAC
PAC
PAC
(a) Exposure to UV light
PAC PAC PAC PAC PAC PAC PAC PAC PAC PAC PAC PAC PAC PAC PAC
PAC
PAC
PAC
PAC
PAC
PAC
PAC
PAC
PAC
PAC
PAC
PAC
PAC
PAC
PAC
PAC
PAC

(c) PEB causes PAC diffusion

Photoresist Technology

Standing

waves

Unexposed Exposed photoresist photoresist PAC PAC PAC PAC PAC PAC PAC PAC PAC PAC PAC
Unexposed
Exposed
photoresist
photoresist
PAC
PAC
PAC
PAC
PAC
PAC
PAC
PAC
PAC
PAC
PAC
PAC
PAC
PAC
PAC
PAC
PAC
(b) Striations in resist

(d) Result of PEB

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Suppression of Standing Wave Effect by BARC

Incident wave

Photoresist Film Substrate
Photoresist
Film
Substrate

Bottom Antireflective coating (BARC)

The use of antireflective

coatings can help prevent interference by reducing the

reflected wave intensity.

Photoresist Technology

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Suppression of Standing Wave Effect by BARC

Mask

Exposed

photoresist

Polysilicon

Photoresist Technology

UV exposure light

Unexposed photoresist BARC STI STI Substrate
Unexposed
photoresist
BARC
STI
STI
Substrate

65

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BARC Phase-Shift Cancellation of Light

(B) Top surface reflection (A) Incident light (C) (D) C and D cancel due to
(B) Top surface reflection
(A) Incident light
(C)
(D)
C
and D cancel due
to
phase difference
Photoresist
BARC (TiN)
Aluminum

Photoresist Technology

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BARC Phase-Shift Cancellation of Light

EE6601 MicroFabrication Technology NTU-EEE-Tse MS BARC Phase-Shift Cancellation of Light Photoresist Technology 67

Photoresist Technology

67

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Suppression of Standing Wave Effect by TARC

Resist-substrate

Incident light reflections Photoresist Substrate
Incident light
reflections
Photoresist
Substrate

Photoresist Technology

Incident light Top antireflective coating (TARC) absorbs substrate reflections. Photoresist Substrate reflection
Incident light
Top antireflective coating
(TARC) absorbs substrate
reflections.
Photoresist
Substrate reflection
Substrate

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Suppression of Standing Wave Effect

The use of BARC

MS Suppression of Standing Wave Effect The use of BARC Post Exposure Bake (PEB) Photoresist Technology

Post Exposure Bake (PEB)

Wave Effect The use of BARC Post Exposure Bake (PEB) Photoresist Technology SEM photographs showing that

Photoresist Technology

SEM photographs showing that ARC process improves linewidth narrowing (right with

BARC) at a step on a

topographic substrate. Linewidth is 0.25µm.

SEM photographs of resist image of 0.35 µm pattern

in 0.98 µm thick i-line resist developed with (right) and

without PEB (left).

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EE6601 MicroFabrication Technology

Proximity effect

NTU-EEE-Tse MS

1D Proximity Effects

For the same feature size on the reticle there will be a different light

intensity on the wafer plane as a result of diffraction. The final printed features depend on feature separation.

wafer plane as a result of diffraction. The final printed features depend on feature separation. Photoresist

Photoresist Technology

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EE6601 MicroFabrication Technology

Proximity effect

Pattern on Mask:

NTU-EEE-Tse MS

2D Proximity Effect

Pattern on wafer:

s k : NTU-EEE-Tse MS 2D Proximity Effect Pattern on wafer: Photoresist Technology Lines shorter Curves

Photoresist Technology

Lines shorter Curves bulge/larger

71

EE6601 MicroFabrication Technology

Proximity effect

NTU-EEE-Tse MS

2D Proximity Effect

Can be fixed by Optical Proximity Correction (OPC)

Effect Can be fixed by Optical Proximity Correction (OPC) Suppression of Proximity Effects : Resolution Enhancement

Suppression of Proximity Effects :

Resolution Enhancement Techniques --- Advanced Lithography

Photoresist Technology

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Environmental Effects

Contamination and Particles

Amine contamination for DUV CA resist

Temperature

Humidity

Vibration

Atmospheric Pressure

Photoresist Technology

73

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Contamination and Particles

Various ways in which dust particles

on wafer and photomask can interfere with photolithography patterns.

Particle directly on wafer can locally disrupt pattern development during a lithographic step

disrupt pattern development during a lithographic step (a) SEM photo of particle on a wafer surface

(a)

SEM photo of particle on a wafer surface (uncovered)

(b)

SEM photo of the same particle covered by overlaying film

SEM photo of the same particle covered by overlaying film Dust particle # 1 & 2

Dust particle # 1 & 2 cause “faults” while # 3 can cause “defect” and device failure

due to short circuit on wafer This

particle becomes a part of the mask

Photoresist Technology

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EE6601 MicroFabrication Technology

Contamination and particles

NTU-EEE-Tse MS

• Conclusion: We need to protect the

wafers against dust and other

contaminants.

• How: By controlling the atmosphere – clean room and mini-environment

the atmosphere – clean room and mini-environment Comparison of nanosize technologies (a) Shrinking

Comparison of nanosize technologies

and mini-environment Comparison of nanosize technologies (a) Shrinking design-rules and the impact of defects. (b)

(a) Shrinking design-rules and the impact of defects.

(b) Illustration of “killer-defects” caused by particle

contamination. (b1) Missing-material in a conductor- line; (b2) extra-material deposited between line. (d) SEM-photo of missing-material in a conductor line.

Photoresist Technology

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EE6601 MicroFabrication Technology

Clean Room

It would not be cost

effective to control the whole working clean room to the most stringent requirement -selected working areas/cells should

be controlled and wafers

should not be exposed to the general cleanroom --- mini-environment and SMIF pod concept especially for the photolithography steps

ISO 14644-1

FED STD 209E

ISO 3

1

ISO 4

10

ISO 5

100

ISO 6

1,000

ISO 7

10,000

ISO 8

100,000

Cleanroom class comparison

Photoresist Technology

NTU-EEE-Tse MS

ISO 14644-1 cleanroom standards

 

particle/m³

Class

0.1 µm

0.2 µm

0.3 µm

0.5 µm

1 µm

5 µm

ISO 1

10

2

ISO 2

100

24

10

4

ISO 3

1,000

237

102

35

8

ISO 4

10,000

2,370

1,020

352

83

ISO 5

100,000

23,700

10,200

3,520

832

29

ISO 6

1,000,000

237,000

102,000

35,200

8,320

293

ISO 7

352,000

83,200

2,930

ISO 8

3,520,000

832,000

29,300

ISO 9

35,200,00 0

8,320,000

293,000

US FED STD 209E cleanroom standards

 

particle/ft³

Class

0.1 µm

0.2 µm

0.3 µm

0.5 µm

1 µm

5 µm

1

35

7

3

1

10

350

75

30

10

1

100

3500

750

300

100

10

1

1,000

1,000

100

10

10,000

10,000

1,000

100

100,000

100,000

10,000

1,000

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EE6601 MicroFabrication Technology

Contamination and particles

conclusions

• Necessary for advanced device processing

• Absolutely necessary for lithographic processes

• The decrease in device features

demands cleaner and cleaner

environments clean room is not enough or too expensive

• Instead, use mini-environments

(SMIF)

Photoresist Technology

NTU-EEE-Tse MS

Mini-environments

Photoresist Technology NTU-EEE-Tse MS Mini-environments • Mini -environments: each machine has its own atmosphere

• Mini-environments: each machine has its own atmosphere and wafers are

transported in special sealed boxes

(SMIF-pods). • SMIF: Standard-mechanical interface

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EE6601 MicroFabrication Technology

Environmental Effect

CA resists has high sensitivity, contrast and resolution.

Appearance of an anomalous insoluble skin and linewidth shift if the PEB was delayed.

Susceptible to the presence of airborne base contamination a yield limiting issue of DUV resists.

Ammonia and other volatile basic compounds can affect the performance of resists used to produce DUV images.

CA resist is susceptible to molecular base (MB) contamination from the moment the resist is coated until the post-exposure bake step in the process.

Pre-exposure basic contamination can cause typically a widening in the top of the image profile called a ‘T-top’.

Since exposure to environmental base contamination causes a change in the image profile, CA resists are said to be environmentally sensitive.

Solution :

chemical filters are employed in DUV lithography

equipment to control the effects of environmental base contamination, viz. T-topping. some CA resists may be affected by impurities in the air at very low levels down to 1 or 2 parts-per-billion (ppb).

Photoresist Technology

NTU-EEE-Tse MS

T-top formation in DUV Chemical Amplified (CA) resist due to delay in Post Exposure Bake (PEB)

(CA) resist due to delay in Post Exposure Bake (PEB) Indiffusion of basic contaminant through the

Indiffusion of basic contaminant through the top surface of the

resist film and its impact showing

T-topping on the resist profile.

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Amine Contamination of DUV Resist

leading to “T-top” Formation

Region of

Neutralized

photoresist

unexposed photoresist PAG H + H + PAG H + PAG H + PAG H
unexposed
photoresist
PAG
H +
H +
PAG
H +
PAG
H +
PAG
H +
H +
PAG
PAG
H +
H +
PAG
PAG
H +
H +

Acid-catalyzed

reaction of exposed

resist (post PEB)

H + H + Acid-catalyzed reaction of exposed resist (post PEB) Resist T-topping Development } Photoresist

Resist T-topping

Development
Development

}

Photoresist Technology

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6. Characterization of Working Windows

Focus Exposure Matrix

Technology NTU-EEE-Tse MS 6. Characterization of Working Windows Focus Exposure Matrix Photoresist Technology 80

Photoresist Technology

80

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6. Characterization of Working Windows

Focus Matrix

Technology NTU-EEE-Tse MS 6. Characterization of Working Windows Focus Matrix Photoresist Technology Focus position 81

Photoresist Technology

Focus position
Focus position

81

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6. Characterization of Working Windows

Exposure Matrix

Photoresist Technology

Exposure Dose
Exposure Dose

82

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6. Characterization of Working Windows

Selecting optimal focus point:

Wafer stage optimal location

Selecting optimal dose:

print bias: mask size to wafer size difference

location • Selecting optimal dose: – print bias: mask size to wafer size difference Photoresist Technology

Photoresist Technology

location • Selecting optimal dose: – print bias: mask size to wafer size difference Photoresist Technology

83

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6. Characterization of Working Windows

Selecting optimal focus point:

Wafer stage optimal location

Selecting optimal dose:

print bias: mask size to wafer size difference

location • Selecting optimal dose: – print bias: mask size to wafer size difference Photoresist Technology

Photoresist Technology

location • Selecting optimal dose: – print bias: mask size to wafer size difference Photoresist Technology

84

EE6601 MicroFabrication Technology

CD Control with DOF

NTU-EEE-Tse MS

Technology CD Control with DOF NTU-EEE-Tse MS Photoresist Technology Negative focus Focus above the

Photoresist Technology

Negative focus Focus above the resist

Positive focus Focus below the resist

85

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CD Control with DOF and Feature Size (L/S)

EE6601 MicroFabrication Technology NTU-EEE-Tse MS CD Control with DOF and Feature Size (L/S) Photoresist Technology 86

Photoresist Technology

EE6601 MicroFabrication Technology NTU-EEE-Tse MS CD Control with DOF and Feature Size (L/S) Photoresist Technology 86

86

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EE6601 MicroFabrication Technology NTU-EEE-Tse MS Photoresist Technology 87

Photoresist Technology

87