NANOFABRICATION

NANOIMPRINT LITHOGRAPHY

Dr. Nikos Kehagias

Head of Nanofabrication division
Catalan Institute of Nanotechnology (ICN)
B
Barcelona
l
Spain

Email: nikolaos.kehagias.icn@uab.es
nikolaos kehagias icn@uab es
 Outline

• Nanofabrication techniques:
¾ Resolution and limits
¾ Alternative nanolithography techniques
¾Nanoimprint lithography: issues, challenges, potentials

• Nanoimprint lithography applications:

¾ Examples of passive photonic devices
¾ Functional materials
¾ 2D PhC devices for enhanced light extraction

• Nanometrology
¾ Non destructive techniques
Nanotechnology: enabling multi-billion
dollar industry
Approach towards Nanotechnology
 Key Requirements of Lithography for
Manufacturing ICs*
• Critical Dimension Control
– Size of features must be controlled within wafer and wafer‐to‐wafer
Size of features must be controlled within wafer and wafer to wafer

• Overlay
– For high yield, alignment must be precisely controlled
For high yield, alignment must be precisely controlled

• Defect Control
– Other than designed pattern, no additional patterns must be imaged

• Low Cost
– Tool, resist, mask; fast step‐and‐repeat 30‐40% of total semiconductor 
manufacturing cost is due to lithography (Masks, resists, metrology)
– At the end of the roadmap, μP will require 39 mask levels

*ITRS 2005/6, Lithography
NANOFABRICATION
METHODS
Fabrication methods for small structures
Decrease in minimum feature size with
time (Moore’s
(Moore s law)
 Nanopatterning techniques

• Nanolithography techniques
• EUV/UV lithography
lith h
• Electron beam lithography
• Focused ion beam lithography
• X-ray
X ray lithography

• Alternative lithography techniques

•Template assisted self assembly techniques
• Micro-contact printing
• Nanostensil technique (nano-mask
(nano mask lithography)
• Ink-jet lithography
• Nanoimprint lithography
 Nanopatterning techniques

Patterningg time for 10% of a 4” wafer as function of obtainable line width for different
lithography techniques. The arrows and the question mark in the NIL bar indicate
that faster imprint times may be obtainable by optimizing the imprint process.
Template assisted self assembly techniques

““Self-assembly”
lf bl ” refers
f to the
h deposition
d off an organized
d layer
l onto a
substrate with a high-degree of control and/or ordering.
 Colloidal self assembly

Set-up

Material: Polymethyl metacrylate with

a mean diameter of 368nm
(<5% polydispersity)
Substrate: Glass
Concentration: 4% wt in de-ionized
water
Acoustic vibration: white noise (40-
4kHz)
Drawing speed: stepping motor at
1.3mm/hr
Colloidal self assembly

Cross section SEM images: 3D ordering

Stochastic resonance-like behaviour

L – noise level
L40 - best

Standing wave formation

at high noise level leads to
locally suppression (or
optimization) of noise
vibration

Local but uncontrollable

i
increase i llattice
in tti ordering.
d i
Block copolymer self assembly
 Requirements for graphoepitaxy
Patterned sidewall material
Mesa width ~ 50 nm - Would like to test both PS
Groove width
(or as narrow as possible) and PMMA wetting walls
40 – 200 nm
- Fab-friendly materials ideal

Wall height ~ 30 nm Base must have surface OH

groups to allow us attach
Neutral
eu a po
polymer
y e bbrush
us

Substrate

Patterned Silicon dioxide Patterned HSQ

 Designed Nanostructures via Templating

Silicon-based trenches and Angled lamellae nanostructures

aligned nanostructures
nanostructures.
 Nanostensil Lithography
The Nanostensil
Th N t il ttechnique
h i iis a patterning
tt i method
th d b
based
d on
shadow mask evaporation

A thin membrane is used as a solid mask to transfer the patterns

from the membrane to the substrate during the evaporation

Full-wafer stencils Side view stencil

 Nanostensil Lithography
Main advantages:
• No resist, development or baking
• Non contact
• Re usable
• Micro and nanostructuring in a single step
• High flexibility of materials (metals, oxides, SAMs)

Challenges:
• Clogging occurs due to the accumulation of
deposited material on top and inside the membrane
apertures.

• Blurring

• Contamination of stensil

• Stiffness of stensil
 Dip-pen Lithography

Ink transfer using a coated AFM tip by capillary effect.

Dip-pen lithography of SAMs
 Introduction to Nanoimprint

Proposed by S.Y. Chou (Minnesota Uni., USA) in 1995

(Appl. Phys. Lett., 67, 3114 (1995))

Idea: a nanometer-size pattern is transfered not by electron, ion or

other beams, but by a stamp via mechanical contact between the
stamp and a substrate with a polymer.

Advantages:
• Cost
C efficient
ffi i
• High throughput
• High
Hi h resolution
l i
• Simple
• Flexible
Fl ibl
 Current Fabrication methods
Electron Beam Lithography Extreme UV Lithography Scanning Probe 
Lithography

Ad t
Advantages Ad t
Advantages Ad t
Advantages

• Very accurate control of  • Extreme UV is 10‐14nm  • Very good control of 

pattern with direct writingg
p wavelength source
g pattern and resolution
p
• No mask needed • Resolution approaching  Approximately 
• Highly automated 30nm 10nm possible
• 5nm resolution possible • High Throughput • Highly automated

Disadvantages Disadvantages Disadvantages

•Very low throughput • Mask fabrication is difficult • Very slow process

Less than 10 wafers per  • Reflective optics can be  • Instrument can be 
hour expensive costly
• Expensive  CaF instead of SiO2 optics • Time of process 
Hardware cost 6‐10 Million
Hardware cost 6‐10 Million • Cost of EUV startup ~50‐60
• Cost of EUV startup  50‐60  eliminates
million industrial feasibility
 Alternative method:Nanoimprint Lithography
• Nanoimprint lithography (NIL) is simple in comparison to alternatives
• High throughput capabilities
• Low cost for a next-generation technology (No need for small λ laser sources
and optics)
• High cost in master mold, but all other molds can be made from this master
Lithography  Resolution  Cost  (M $) Throughput Feasible
(nm) 
248 nm  90  8 √ √
193 nm 45 20 √ √
157 nm 32 50 √ √
EUV
EUV  16 100 √ √
Ebeam 10 5‐10 x √
Imprint 14 1 √ √

R&D machines can be  1 master Æ10.000 sub mastersÆ100 million disks
purchased for 100k  $250.000Æ $1.000 eachÆ10c per disk for mask cost
 Nanoimprint enables multiple billion dollar
industries
MEMS/NEMS

Displays Wireless Com.

Com

NIL
Data storage Etc.

Biotech Semicond. IC’s

Pharmaceutical
 Nanoimprint Lithography (NIL)
Stamp (Si
(Si, Quartz
Quartz, etc) Advantages

Resist (polymer, monomer) • Resolution (sub 10 nm)

Substrate • Fast (sec/cycle)
• Low
L costt ($0.2M
($0 2M vs $25M)
• Simple
Imprint • Flexible (UV, heat)
(Pressure +heat or UV light)

Applications

Release • Semiconductors
(
(cool
lddown ) • Optics
O ti
• Bio
• Organic electronics
RIE of residual layer • Sensors

High resolution Complex patterns Functional devices

 Multimode NIL
Thermal  Reversal NIL  Reverse UV NIL 
Transparent stamp with metal protrusions

UV light, pressure, heat

Inking Whole layer transfer

Development

Single NIL tool capable of multiple modes pattering/fabrication

Highly versatile, yet simple, nanofabrication tool

Step & Stamp/flash NIL

NPS 300 Nano imPrinting Stepper
• Thermal + UV nanoimprinting
• Up to 300 mm wafers
• Sub‐20 nm features
S b 20 f t
• 250 nm overlay accuracy
• Automatic alignment

~ 10 nm holes in polymer
T. Haatainen et al., VTT 2001
 Step and Stamp nanoimprint lithography

In liquid alignment:
Pre- and post-exposure.

Defects caused due to material

failure in small features with large
S.V. Sreenivasan et. al., Semiconductor Fabtech, 25th ed., 111, 2005. feature height.
 Roll-to-Roll NIL
Bendable Ni stamp 

AFM images of stamp and imprint

• Printing speed from 0.3 to 20 m/min

• Line depth of 151 – 112 nm 

• Min feature at 5m/min is 50 nm
Min feature at 5m/min is 50 nm

Courtesy of T. Mäkelä et al., VTT, Finland
 Roll to roll NIL

Se Hyun Ahn et al., ACS Nano, 3, 8, 2304, 2009 Adv. Mater. 2008, 20, 2044–2049
Polymer stamps
 State of the art of NIL techniques
Smallest/ Min Largest Overlay t align,
largest pitch wafer Accuracy t print,
features in (nm) printed (nm) t release,
same print (mm) t cycle

NIL 2 nm, Minutes,

10s, Min,
N/A 14 200 500
10-15 min

Full cycle 2.5

8 nm, min
i with,
ith 20 s
SSIL 50 nm/5 µm 50 200 250
without full
auto
collimation.

10 nm 50 300 50 20
SFIL 25 nm/ µm wafers/hr

UV-NIL 9nm/100µm 12 200 20 20s/step

3 wafers/hr

Soft
S ft UV
UV- 4-5
4 5 min
i ca.
25nm/ 20µm 150 200 1-50µm 12wafer/hr
NIL
 NIL issues and complications
NIL
NIL metrologies critically needed:
t l i iti ll d d Blazed gratings
• Critical Dimension measurements of sub‐50 nm features
• Quantify fidelity of imprint pattern transfer
• Feedback on pattern quality needed to engineer and optimize NIL
db k li d d i d i i

NIL materials science :

• Resist material selection is done empirically Tearing of pillars
• Guidelines for imprinting functional materials?
Guidelines for imprinting functional materials?
• Imprinted nanostructures may have different properties
• Possible orientation and anisotropic properties
• Low temp and low pressure
• Minimal shrinkage
• Mechanical strength and tear resistance
• Mold fill  Æ Viscosity
• Tg 
• Tg for thermoplatic resist (imprint usually done 70
for thermoplatic resist (imprint usually done 70‐80°C
80 C above T
above Tg)
 NIL issues and complications
Template

• Usually fabricated from Si, quartz, or nickel
• Critical dimension control
• Critical dimension control
• Defect free fabrication & Inspection
• Adhesion and use of antisticking coating on template
• Cleaning & re‐use
• designing for imprint uniformity –> Uniform residual layer

Courtesy of Dr C Gourgon (CNRS‐LTM)

Courtesy of Dr C. Gourgon (CNRS LTM) 

Overlay accuracy
Moiré concentric circles 
• NIL has no distortion due to lens (since no lens is used)
NIL has no distortion due to lens (since no lens is used)
• Smaller error budget for template pattern placement Aligned 
• Mask/template distortion due to pressure and/or 
temperature & defects

Misaligned 
 Principles of NIL
T‐P vs. time diagram of NIL process 
Stamp
Polymer layer (a)
Substrate

Heat

Apply pressure (b)

Cool down
Demolding 
Separate (c)

Residual layer (d)

Etch residual
(e)
layer
Viscosity dependance on MW, P and T

MW dependance
MW dependance
⎧Μ , M < Mc
η 0 ∝ ⎨ 3.4± 0.2 Temperature 
⎩Μ , M > Mc dependance
C1 (T − Tg ) η (T )
log aT = − = log 0
Pressure dependance C 2 + T − Tg η 0 (Tg )

Δ ln η − 2 Δ ln η William Landel Ferry equation 
≈ −4 × 10
ΔP (bar ) ΔT
Squeeze flow theory during a typical NIL process
z

Stamp z wi
S S/2
h pr
Polymer
l x vy=0 vy((z))
y h(t)
Substrate

N N N

Continuity equation:  ho ∑ (s i + wi ) = h f ∑ (si + wi ) + h pr ∑ (wi )

i =1 i =1 i =1

Navier Stokes equation:  ∇p = η 0 ∇ 2 u
Residual Polymer height  Estimated imprinting time 

1 1 2 F pr ηο s 2 ⎜⎛ 1
1 ⎞
⎟
= 2 + t tf = − 2
2
h (t ) h0 n0 Ls 3 ⎜ 2
2 P ⎝ h f ho ⎟
⎠
H. Schift and L.J. Heyderman, Nanorheology“. 
Chapter 4 in, Alternative Lithography“, ed. C. Sotomayor‐Torres. Kluwer Academic (2003).
 Polymers used in NIL

Material Glass Molecular Viscosity Solvent

transition weight
g
Temperature
PMMA 105 oC 75k 10 ± 2 Anisole
(mPas)
mr-L 6000 40 oC 7k 2,4 ±1 PGMEA/
mr-NIL 6000 (mPas) Anisole
mr-II 7000
mr 60 oC 120k 4±2 PGMEA
(mPas)
mr-I 8000 115 oC 120k 5±2 PGMEA
((mPas))
Polystyrene 100 oC 50k - Toluene
(PS)

Typical refractive index values for polymer are between 1.3 ‐ 1.6
 Functional polymers

Polymers with embedded NC’s (CdSe, CdSe, etc.), 
NP (Au, TiO
( , 2 etc.), Dyes (Rhodamine etc.)
2,  ), y ( )

Polymers with embedded NP (Au, TiO2, etc.)

Surface modification of  polymers (nanoparticle deposition, 
change of the polymer surface tension, etc.)
h f th l f t i t )

[ -6.63V -> -3.96V ] -9.02V -> -1.99V [V]

-2.00

5.00
-3.00

Di‐block co‐polymers (PS‐b‐PMMA) -4.00

-5.00

[ µV ]
-6.00

-7.00

-8.00

-9.00

0
0 [ µV ] 5.00

Conductive polymers (polypyrrole, polyaniline etc.)
NIL process challenge: imprint quality
control
 Fundamental process challenges

Critical Dimensions
Critical dimensions (CD)
Critical dimensions (CD) 
Width Height

Slope
Residual layer
1 μm

Residual layer thickness and uniformity 
over large areas (> 300mm) Residual layer

100 nm
 Nanoimprint lithography process

Stamp Stamp with different size protrusions

Polymer layer
Substrate

Heat

Imprint
C l down
Cool d
Stamp bending

Separate

Etch residual
layer Different filling factors Æ lead to
inhomogeneous residual layer
 Photonic circuit

Combination of variable scale features on the same stamp

 Mathematical model

The resist movement is determined by the 2D pressure distribution P(x,y,t) calculated from the following
problem:

{ 3
}
∇ [D( x, y ,t ) + h( x, y )] ∇P ( x, y ,t ) = 12η
∂D( x, y ,t )
∂t
, ( x, y ) ∈ Ω f , t ∈ (0,T ], P ( x, y ) = 0, ( x, y ) ∈ Ω / Ω f ,
(1)
t
D( x, y ,t ) = d0 − ∫ Vst (ζ ) dζ + δ st ( x, y ,t ) + δ sb ( x, y ,t ),
0

where d0 is the initial resist thickness; h is the stamp relief height; δst and δsb are the normal displacement
of the stamp and substrate surface, respectively; Vst is the stamp velocity; T is the duration of the
imprinting process; η is the dynamic viscosity of the resist; Ω is the considered domain of the stamp; Ωf is
the part of Ω, in which all cavities are filled with the resist.
q
Equations ((1)) is derived from 3D Navier-Stokes equations
q with the understanding
g that the resist motion is
largely directed along the substrate surface.
For the calculation of δst and δsb, the stamp and the substrate are represented as semi-infinite regions (an
elastic medium bounded by a plane). In this case, the elastic normal displacement is described by the
following expression:

1− σ 2 P ( x ′, y ′,t ) dx ′dy ′
δ ( x, y ,t ) =
πE ∫∫
Ω ( x − x ′) + ( y − y ′)
2 2
, ( x, y ) ∈ Ω, t ∈ (0,T ],

where
h σ is
i Poisson's
P i ' ratio
ti and
d E is
i modulus
d l off elasticity.
l ti it
 Experimental parameters

Polymer used: PMMA and mr-I8030E

Initial polymer thickness: 340 nm and 318 nm
Imprinting
p g temperatures:
p 180 oC - 200 oC
Dynamic Viscosity : 2×104 Pa⋅s @ 180°C and 3×103 Pa⋅s @ 200°C.

Chirped grating structures stamp was used

Stamp relief: ~300 nm
Stamp design

Simulation parameters:
• stamp velocity:1 nm/s,
• duration of the imprinting process: 268 sec
• grid size:128×128 pixel

Instruments used:
• Dektak profilometer (Veeco instruments)
• Reflectometer
 Resist PMMA 75K.
Imprinting parameters: the stamp cavities depth - 300 nm, the initial resist thickness - 340 nm,
the imprint temperature - 190°C, the resist viscosity - 104 Pa⋅s.

Experiment Simulation

500

400
experiment Comparison
p of measured and
simulation
H, nm

300 simulated values of resist

thickness
200
Accuracy
100
1.5% 1.3% 2
2.6%
6% 2
2.1%
1%
0.5% 0.5% 1.5%
1 9% 2
1.9% 2.4%
4% 2 4%
2.4%
0% 0%
0
0 2 4 6 8 10 12
zone number
Resist mr-I 8000 (Micro Resist Technology GmbH).
Imprinting parameters: the stamp cavities depth - 300 nm, the initial resist thickness - 318 nm,
the imprint temperature - 180°C, the resist viscosity - 2×104 Pa⋅s.

600

500

400

H, nm
300

200

100 simulation
experiment
0
-4200 -4000 -3800 -3600 -3400 -3200 -3000
x, μm
(a) (b)

600 600

500 500

400 400
H, nm

H, nm
300 300

200 200

100 simulation 100 simulation

experiment experiment
0 0
-4200 -4000 -3800 -3600
x, μm
-3400 -3200 -3000
(c) -4200 -4000 -3800 -3600
x, μm
-3400 -3200 -3000
(d)

((a)) The
Th optical
ti l microscopy
i i
images off the
th test
t t structure
t t i
imprinted
i t d in
i the i t att 180°C. Horizontal
th resist H i t l color
l lines
li
indicate zones of profilometer measurements of resist thickness. White isolines specify the calculated
distribution of the stamp/substrate deformation (numbers signify the elastic displacement in nanometers). (b)-
(d) Comparison of measured and simulated profiles of resist thickness for the test structure.
Resist mr-I 8000 (Micro Resist Technology GmbH).
Imprinting parameters: the stamp cavities depth - 300 nm, the initial resist thickness - 318 nm,
the imprint temperature - 200°C, the resist viscosity - 3×103 Pa⋅s.

600

500

400

H, nm
300

200

100 simulation
experiment
0
-4400 -4200 -4000 -3800 -3600 -3400 -3200
x, μm
(a) (b)

600 600

500 500

400 400
H, nm

H, nm
300 300

200 200

100 simulation 100 simulation

experiment experiment
0 0
-4400 -4200 -4000 -3800
x, μm
-3600 -3400 -3200
(c) -4400 -4200 -4000 -3800
x, μm
-3600 -3400 -3200
(d)

((a)) The
Th optical
ti l microscopy
i i
images off the
th test
t t structure
t t i
imprinted
i t d in
i the i t att 200°C. Horizontal
th resist H i t l color
l lines
li
indicate zones of profilometer measurements of resist thickness. White isolines specify the calculated
distribution of the stamp/substrate deformation (numbers signify the elastic displacement in nanometers). (b)-
(d) Comparison of measured and simulated profiles of resist thickness for the test structure.
 Viscosity estimation for resist mr-I 8000 at 180°C.
the resist dynamic viscosity = 3 ×103 Pa⋅s the resist dynamic viscosity = 10 4 Pa⋅s

500 500

400 400
H, nm

H, nm
300 300

200 200

-4800 -4600 -4400 -4200 -4000 -3800 -3600 -3400 -3200 -3000 -2800 -4800 -4600 -4400 -4200 -4000 -3800 -3600 -3400 -3200 -3000 -2800
x, μm x, μm

the resist dynamic viscosity = 2 ×104 Pa⋅s

500

400
H, nm

300

200

-4800 -4600 -4400 -4200 -4000 -3800 -3600 -3400 -3200 -3000 -2800
x, μm
The best fit of simulation results to the experimental data.

the resist dynamic viscosity = 3 ×104 Pa⋅s the resist dynamic viscosity = 10 5 Pa⋅s

500 500

400 400
H, nm

H, nm

300 300

200 200

-4800 -4600 -4400 -4200 -4000 -3800 -3600 -3400 -3200 -3000 -2800 -4800 -4600 -4400 -4200 -4000 -3800 -3600 -3400 -3200 -3000 -2800
x, μm x, μm
NIL Potentials
Intel microprocessor-Brief history
Intel microprocessor-Fabrication steps

35 nm
35 nm Three dimensional Si stamp for NIL applications 
 3D nanofabrication techniques
C
Conventional methods:
ti l th d

Electron beam Focused ion beam Two photon polymerization

Non‐conventional methods:

Combination of NIL and X‐ Combination of lithographic  Reverse NIL

ray Lithography steps and wet etching
 3D nanofabrication techniques

Direct patterning of three dimensional structures by NIL

Transistor Metal T‐gate with  3D‐Hot embossing of  Triangular Profile Imprint

90 nm wide foot  undercut structures

M. Li et. al N. Bogdanski et. al Z. Yu et. al

3D nanofabrication techniques

Towards three dimensional photonic crystals

Woodpile‐like structure

Determistic defect
Reverse UV NIL technique

Selective Transfer mode
 3D woodpile like structures
1 Layer 2 layers

1 μm
10 μm

3 layers

4 μm