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Lithography 2

(includes photolithography,
electron beam lithography,
x-ray lithography and ion
beam lithography)
EEET2045/2155
General References
• Nanotechnology for Chemical Enigneers, Said Salaheldeen Elnashaie
Firoozeh Danafar Hassan Hashemipour Rafsanjani Springer ISBN
978-981-287-495-5
• Introduction to Nano Basics to Nanoscience and Nanotechnology
Amretashis Sengupta Chandan Kumar Sarkar Springer ISBN 978-3-
662-47313-9
• Introduction to Surface Engineering and Functionally Engineered
Materials Peter M. Martin Scrivener Publishing ISBN:
9780470639276
• Materials and Processes for Next Generation Lithography, Volume 11
1st Edition Alex Robinson Richard Lawson Elsevier ISBN:
9780081003541
• Fabrication and Characterization in the Micro-Nano Range New
Trends for Two and Three Dimensional Structures Fernando A.
Lasagni Andrés F. Lasagni Springer ISBN 978-3-642-17781-1 2
Photolithography process
• Photo-resist is deposited on
clean wafer
• The resist is exposed to light
through a mask
• The mask is typically made
from Quartz due to it’s
superior transparency in the
UV and Chrome
• After exposure the
photoresist is developed
using a series of baking steps
and exposure to chemical
developing agents
• When positive photoresist is
used the exposed resist is
removed, for negative
photoresist the exposed areas 3
remain
Chemistry of g and i-lines DNQ (or DQN) Positive Resists
POSITIVE DNQ PHOTORESIST for g and i lines
consist of three major components and other additives and stabilizers
Component 1. Matrix material (N) or Base (inactive) Resin (e.g. novalac). The N part of DNQ

=>hydrophilic ( due to OH group). Novolac itself is soluble in aqueous alkaline developer.


The matrix material determines the mechanical properties of the photoresist film. Novolac
has a long chain polymer consisting of hydrocarbon rings with 2 methyl groups and 1 OH
group attached. The basic ring structure may be repeated from 5 to 200 times.

Component 1. Base - Novolac.

Component 2. Solvent (e.g. PGMEA, 1-methoxy-2-propyl acetate), used to adjust


viscosity. After spinning and baking resists ~ 1:1 PAC (component 3, see next slide)
and resin(matrix). If this ratio is ~1 then the photoresist is almost insoluble in a base
solution.
Continued
Component 3. Photoactive compound/ PAC (e.g. diazoquinones/DQs are the most common)
=>acts as dissolution inhibitor (DQ is hydrophobic) in typical developers, when it is not exposed to
UV radiation. Reduces the dissolution rate of unexposed resists to ~ 1- 2 nm sec-1. The unexposed
PAC reduces the dissolution rate of the resist in the developer by a factor of 10 or more. This occurs
by a chemical bonding of the PAC and the Novolac at the surface of the resist where it is exposed to
the developer. Although the exact mechanism is still subject to debate [Campbell].
=>acts as dissolution promoter (carboxylic acid is hydrophilic) when it is exposed (bleached)
by UV radiation. This allows the developer to wet & penetrate the resist during development.

PACs are often diazoquinones.


The photoactive portion is above the SO2.

Continued
Continued Component 3. Photoactive compound/PAC (e.g. diazoquinones/DQ,)
=>photolysis occurs upon expose to UV, carboxylic acid is formed and the resist loses its
dissolution-inhibition function. As a result, the resist becomes soluble in alkaline aqueous
solutions.

Diazoquinone. The N2 in
the PAC is weakly bonded. The
addition of UV light frees the + UV light
N2 leaving behind a highly
reactive carbon site. It
becomes stabilised by one of
the carbons moving outside
the ring. The oxygen atom is PAC (DQ)
then covalently bonded to this
carbon. The process is known
as a Wolfee rearrangement.

After the Wolfee rearrangement,


the molecule is called ketene. In
the presence of water, a final + water
rearrangement occurs in which
the double bond to the external
carbon is replaced with a single
bond and an OH group. The final Dissolution ketene
product is carboxylic acid. Enhancer
Chemistry of Chemically Amplified (CA) Resists
•For Deep UV (DUV) (193 nm <  < 289 nm ) exposure systems => Cd lamp (240 nm);Cd-Hg or
microwave Hg(200-500 nm);Xe-Hg (200-400nm);Xe flash (200-500 nm);Br2 (180 nm) etc
•CA resists can be made in positive working or negative working mode.
•Advantages => better sensitivity to exposure, higher resolution and contrast than DNQ resists.
•Drawbacks =>need better environmental and manufacturing controls.
•Upon exposure, the PAG part reacts with incident photons to create an acid molecule.
•The response is mainly catalytic reaction carried out by the subsequent reaction of the
added Photo-Acid Generator (PAG) with the post exposure bake (PEB).
•In positive resist, PAG initiates photo- and thermo-chemical reaction that render the
exposed region soluble in the developer.
•In negative resist, upon exposure and the subsequent bake, PAG causes the exposed region
to crosslink and become insoluble in the developer.
•The process is graphically depicted follow:

Polymer chain
Polymer chain hv Polymer chain PEB
(+ve resist =>soluble
-ve resist =>insoluble)
PAG acid

Continued
Photolithography - negative resist
• SU-8 is one of the most common negative
photoresists
• When activated by light a photoacid produces
protons which open the epoxy groups, resulting in
a reactive intermediate state
• The reactive sites crosslink the monomers during
baking, creating a polymer network
• The polymerized material is insoluble, while the
non-exposed monomer can be washed away

Photoacid Polymerization SU-8 monomer 8


Photolithography - positive resist
• PMMA (Poly(methyl methacrylate),
sulfones and others are commonly used
• Light breaks down the polymer chain
and/or changes the molecular structure to
enhance solubility

PMMA
Referencehttp://henderson.chbe.gatech.edu/Introductions/intr 9
o%20to%20e-beam%20lithography.htm
Summary of DNQ and CA resist exposure process
DNQ resists consist of :
(i) a base resin (a polymer)
(ii) Solvent (which is removed before exposing a resist film)
(iii) Photoactive Compound (PAC).
Before exposure the DNQ resist is insoluble in the aqueous-alkaline developer.
After exposure to near UV light the PAC chemically alters the exposed resist and they
become soluble in the developer. The exposed areas react with the water in the
developer and form carboxylic acid which dissolves in the alkaline part of the
developer. Diazonaphthoquinone or DNQ resists are commonly used today for g-line
and i-line resists.

CA resists consists of :
(i) a base resin (polymer)
(ii) Solvent (which is removed before exposing a resist film)
(iii) Photo-Acid Generator (PAG)

The PAG reacts with the UV light to create an acid molecule which acts as a catalyst
during the PEB (e.g. 120 C for 2 minutes). The key point is that the reaction is
catalytic – the acid molecule is regenerated after each chemical reaction and may
thus participate in tens or hundreds more reactions. Heat is required to drive the
chemical reactions between the acid molecules and the insoluble polymer in order to
make it soluble in the developer.
Defining parameters
• Thickness of the resist
can influence the final
dimensions (remember
DOF)
• Setup of the mask
aligner, resist thickness
and the quality of the
light source will affect
size of over and under
cut
• Molecular photoresists
can achieve better wall
smoothness than
polymer based resists

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Photoacid diffusion

• Most photoresist formulations


are chemically amplified
resists
• the amplifier (i.e. photoacid)
catalyses a reaction during the
post exposure bake (PEB)
• Diffusion of the acid into
adjacent areas leads to
variations in feature size

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Standing Wave Effects in Resist
No standing wave Standing wave

=> caused by topographic reflection & interference


=>resulted in strongly and weakly exposed region along resist edges.
=>minimise by using multiple wavelengths exposure, PEB, light absorber, anti-reflection
coating, transparent chuck at the aligner.

continued
continued
STANDING WAVE EFFECT

continued
continued
STANDING WAVE EFFECT
=> caused by topographic reflection & interference
=>resulted in strongly and weakly exposed region along resist edges.
=>minimise by using multiple wavelengths exposure, Postexposure bake, light absorber,
anti-reflection coating, transparent chuck at the aligner.

photoresist

silicon

continued
continued

Standing Wave Effect, poor contrast and ‘Tricks’ to form overhang


contamination
photoresist

photoresist

‘Tricks’ are used in


photolithography. Here the
Standing photoresist was soaked in
wave chlorobenzene before developing.
effect and This hardens the top of the film
photoresist poor and it develops more slowly.
adhesion Compare the sidewalls with the
other figures.

continued
continued

Good photoresist
patterns Photoresist trench

photoresist

Silicon wafer

Photoresist ridge

‘Tricks’ to reduce the standing


wave effect include using
several wavelengths for
exposure and doing a post
exposure bake (PEB) which diffuses
the high intensity nodes of any
standing wave
Current limitations
• Current commercial lithography uses deep UV light (DUV) provided by
excimer lasers with a wavelength of 193 nm
• Reduction of the wavelength to below 190 nm was ultimately not pursued
until now since no alternative to quartz lenses could be found
• Multiple exposure processes together with immersion lithography allowed to
reduce the feature sizes and separation to give a resolution down to about 40
nm
• Today typical manufacturing can include over 50 lithography steps which is
extremely expensive.
• As a result new technologies working with lower wavelength are investigate.
Many of these technologies are already routinely used in laboratories but are
waiting to be implemented on industrial scale.

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Technology Roadmap

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Extreme UV lithography
• Extreme UV is the wavelength region between 10 and 120 nm
• The wavelength most commonly investigated is 13.5 nm produced by Sn plasma
• All matter absorbs in this region resulting in the need of using Vacuum processing
• Quartz optics can not be used. Interference mirrors of alternating layers of Mo and
Si are used for the optics instead. The best EUV optics absorb ~30% of the light.
Having multiple reflection steps leads to over 95% of the light being lost
• Energy consumption of an EUV system is expected to be over 100 times higher
when compared to DUV to make up for the absorption loss
• 13.5 nm photons have an energy of 92 eV while 193 nm photon has 6.4 eV
resulting in photoelectrons with 80 eV energy. These photoelectrons scatter in the
film creating secondary electrons reducing resolution.
• The flux density to achieve a dose of 15 mJ/cm2 is 10 photons/nm2 (EUV, 13.5
nm) while it is 146 photons/nm2
• The chemistry in the resist resembles both electron and photolithography

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Effect of Photoelectrons and
secondary electrons
• Electrons can travel quite far within the
resist and expose the surrounding areas
• Chemically amplified photoresists that
contain a photoacid, which catalyses a
reaction, are usually used
• The RLS trade-off describes how the
Resolution R is dependent on the line
edge roughness L and the photoresist
sensitivity S.
• Significant work is being dedicated to
develop better photoresist.
• Typical resists with a sensitivity of 40-15
mJ/cm2 achieve a line edge roughness of
2.5-4 nm and a half pitch of 16-22 nm
• Despite these limitation EUV is the main
candidate for 7 nm fabrication
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Effect of low photon flux
• EUV lithography uses high energy
photons, resulting in low photon flux at
a set dose
• If very few photons are absorbed the
pattern may become quite irregular.
Due to non-uniform photoacid
distribution
• Particularly the line edge roughness can
suffer

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X-ray Lithography
• Photons with a wavelength of 1-2 nm are used or 0.1 nm in the case of
deep X-ray lithography
• The light source is usually a compact synchrotron source
• Masks are made from Silicon Carbide (x-ray transparent) with Gold or
Tungsten to block the beam
• Despite having a small wavelength the resolution is limited by
secondary electron generation leading to resolution similar to EUV
lithography.

• The cost of the light source is prohibitive

http://lynceantech.com/technology/x-ray-
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synchrotron/the-compact-light-source.html
Electron Beam Lithography
• Electrons are much heavier than
photons
• As a result the wavelength at a given h Planck’s constant (6.626 x 10-34 J s)
energy is much smaller in the range of m electron mass (9.109 x 10-31 kg)
pm e electronic charge (1.60 x 10-19 C)
V accelerating voltage (0.5 – 3 x 104 V)
• The resolution is not limited by
diffraction but rather by the
interaction and chemistry within the
resist
Simplified to:
• EBL is widely used in research and to
manufacture photolithography masks
• Fabrication of a single wafer can take
Voltage (kV) of λ (nm)
hours to days (depending on feature
5 0.0173
size) while photolithography can
pattern thousands of wafers in a day 10 0.0122
200 0.0027
Light 400 - 700
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Electron Beam Lithography
• Dedicated systems can cost millions, while for research commercial SEM
systems can be upgraded for ~$100K
• EBL is usually conducted without a mask by directly writing with the electron
beam into the resist
• Alternatively in focused electron beam induced processing (FEBIP) a reactive
gas is introduced into the vacuum chamber resulting in either etching or
deposition (i.e. metals) on electron beam exposed areas

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Overview of electron interactions
• Elastic scattering results in heating of the target but does not result in a
reaction
• Interactions that lead to a chemical reaction (exposure) are electron
attachment and electron impact ionization
• Below are possible reaction pathways for a generic molecule AB where A and
B are possible fragments

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Electron penetration depth
• Upon impact electrons are
scattered within the resist
• Backscattering at the substrate
(i.e. wafer) is an issue
• A sweet-spot exists for energies
between 10 and 100 eV

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State of the art EBL examples

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EBL Photoresist
• EBL photoresist also exists in positive and negative tone
• Electron interaction can lead to bond cleavage or reactive intermediates that
result in cross linking
• Chemically amplified resists are avoided for high resolution word to avoid
photoacid diffusion
• New resist materials are being developed that help increase resolution

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Ion beam Lithography
• Typical ion beam lithography
involve protons, helium, neon
or gallium ions, with gallium
being the most common
• At RMIT we have access to
helium, neon and gallium ion
beams
• The operation mechanisms are
similar to electron beam
lithography/ microscopy
• The resolution can be
increased to sub nanometre
• Processing times are
extremely slow and as such
the ion beam lithography is
mostly used for research only

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Ion beam wavelength comparison
• Due to the high mass of
the ions the wavelength
of the ion beam is much
smaller than what is
observed for electrons
• As a result we can work
with significantly less
energy and still have
extraordinary resolution

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Ion beam interactions
• The ion beam interacts with the
substrate/resist via either nuclear stopping,
transferring the momentum to the target
nucleus
• Or via electronic stopping via interaction
with the target electrons
• The transferred energy in electronic stopping
is small since mion>>me-
• When the beam enters the surface
interactions are primarily electronic
stopping, once the energy has reduced
significantly nuclear stopping occurs
• Interactions generate low energy secondary
electrons. These electrons cause the reactions
in the resist
• The secondary electrons have much lower
energy when compared to EBL resulting in
less straggle and higher resolution
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IBL and EBL comparison
• The interaction volume of ion beam lithography is orders of
magnitude smaller than that of electron beam lithography

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Dose dependent damage
• The ion beam
deposits atoms inside
the substrate.
• At high dose defects
and even bubbles are
seen
• Ga ions will impact
the properties of
semiconductors
significantly through
ion implantation
(doping)

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Some examples of Ion beam
lithography
• Feature sizes below 10 nm
are easily achieved
• Feature sizes below 1 nm
have been reported
• Exotic devices may be
fabricated demonstrating
and exploiting quantum
phenomena
• Apart from ion beam
lithography ion beam
milling can also be used
for resist less etching

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Making 3D structures
• Dynamic mask stereo
lithography is often used
• Pixels on the dynamic
mask are either reflective
(white) or non-reflective
• The image is projected
through the transparent
bottom of the reactor
vessel
• Light absorption solidifies
the photoresist
• After each layer the sample
is lifted up 36
Two photon absorption
polymerization
• Specific resist media are
used that only polymerize
when excited by two
photons
• Extremely high light
intensity is needed to
achieve significant
concentrations of double
excited states
• The Femtosecond lasers
can offer high enough
intensity
• 3D printing is achieved by
shifting the focus of the
beam
• Resolution of 100 nm has
been demonstrated
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Examples of natural and
synthetic 3D structures

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3D structures
• 3D structure can be used to
minimize material usage
while maximizing strength
in desired directions
• Potential applications are
mostly biomedical,
including tissue grafts and
bone replacement

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