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Molecular
Printing: A
Chemist’s
Approach to a
“Desktop Fab”
Molecular
Printing: A
Chemist’s
Approach to a
“Desktop Fab”
Chad A. Mirkin
Northwestern University
Department of Chemistry and
International Institute for
Nanotechnology
Modern Printing Tools Revolutionized
the World
It is exceedingly difficult to print with molecules and many materials
on the “nanometer scale”
Information transfer, the semiconductor industry, the microelectronics
revolution, and gene chips
Desk Top Printer
Is It Possible to
Create A “Desk
Top Fab”?
Dip Pen Nanolithography (DPN)
Attributes of DPN: • Direct-write
• High resolution: 10 nm line width, ~5 nm spatial resolution
• Positive printing
• Writing and imaging with same tool
• Molecule general
• Substrate general
• Serial or massively parallel
The NSCRIPTORTM
An Integrated DPN System
Destructive
Delivery of
Energy
Constructive
Delivery of
Materials
Nanografting
Nanoshaving
Anodic Oxidation
“Millipede”
DPN
Scanning Probe Lithography: A
Dichotomy is Emerging
Sol Gel Materials
4mm
290 nm
Dip-Pen
Nanolithograpy
Hard Materials
Nanoparticle Arrays Silicon Nanostructures
12 nm
Nanogap Electrodes
1 mm
500 nm
~45 nm
90 nm
85 nm
100 nm
135 nm
185 nm
Silver Nanostructures
Gold Nanostructures
Single-Walled Carbon
Nanotubes
Virus Nanoarrays
Ultrahigh Density DNA Arrays
Combinatorial DPN Templates
Bio-nanoelectrics
Protein Nanoarrays
Small Organic Molecules
100 nm
4mm
Protein Nanostructures
Conducting Polymers Soft Materials
550 nm 550 nm
4 µm
Polymer resists
The Ultimate in High Density Arrays
Biological Nanoarrays:
• More than just miniaturization with higher density
• New opportunities for biodetection and studying biorecognition
• Templates for guiding the assembly of larger building blocks
• Open up the opportunity to study multivalency and surface cooperativity
Robotic Spotter
(1 Dot/200x200 mm2)
High Resolution DPN
(100,000,000 Dot/200x200
mm2)
Feedback Controlled Lithography
(100,000,000,000 Dot/200x200 mm2)
Conventional Microarray
Low Resolution DPN
(50,000 Dot/200x200 mm2)
Can DPN be Used To Generate Multicomponent
Templates that are Used to Recognize and Larger
Biological structures and Organisms?
Protein (Human IgG)
Virus (HIV)
8.5 nm 120 nm
Living Cells
Spores (Anthrax)
~20 µm ~15 µm
Single Virus Nanoarrays
DPN-Generated Biological Nanoarrays
Multicomponent DNA
Nanoarrays Phospholipid Arrays
Multicomponent Protein
Nanoarrays
Cell Arrays on Nanopatterned Substrates
• Sub 50 nm many mm resolution
• Large Array Patterning
• Multi-component Patterning Capabilities
• Reconstructing the extracellular matrix at the nm scale
5 mm 4 mm
4 mm
80 mm
DPN Generated Positive Photomasks
DPN
ODT
Au Etch
Cr Etch Au Etch
Quartz
Cr Au
Cr Photomask
-1.0 -0.5 0.0 0.5 1.0
-0.8
-0.4
0.0
0.4
0.8
Empty electrode
PPY nanotube
PPY nanotube with UV
Curr
ent (n
A)
Voltage (V)
Device Characterization Replicated Au Electrode
Jang et al, Small, 2009, 5, 1850
DPN Spot Size Is Independent of
Applied Force
Molecular diffusion from point source is independent of applied
force between tip and surface.
1.5 mm
20×90 µm
NanoPrint Array II: 55,000 tips ~ 1 cm2
Pen fabrication yield >99% (preliminary)
In collaboration
with J. Fragala, NanoInk
100 mm
5 µm
400 nm
100 nm
40×40 dots at 400 nm pitch
~88 million features in ~20 min
Polymer Pen
Lithography
(2008)
Hard-Tip, Soft
Spring Lithography
(2011)
Beam Pen
Lithography
(2010)
Cantilever-Free Cantilever-Based
DPN
(1999)
2D 55,000 Pen
Cantilever Array
(2006)
1D Multipen
Cantilever Array
(2000)
Key Advance 1:
Deposition of
materials
rather than
energy
Key Advance 2:
Use an elastomeric
pyramid on a solid
backing for cantilever-
free printing
Key Advance 3:
Move the “spring”
from the tip to a
polymer backing
layer Thermal DPN
(2004)
Giam, et al. Angew. Chem. 2011, 50, 7482.
Scanning Probe Block
Copolymer Lithography
(2010)
Development of Cantilever-Free
Scanning Probe Lithography
PDMS Pen Array Fabrication
Huo, F et al. Science. 2008, 321, 1658.
11 Million Pen Polymer Array
(A)11 million pen array. (B) SEM image of the polymer pen array. (C) An etched gold pattern on a
4 inch Si wafer. (D) Optical microscope image of gold patterns.
A B
D C
Huo, F et al. Science. 2008, 321, 1658.
High Resolution
High Throughput
Mask-free Nanofabrication
Huo, F et al. Science. 2008, 321, 1658.
Polymer Pen Lithography (PPL)
100 circuits in
1 cm2 with 500
nm and 100
µm features
100 μm
500 nm
Printing Circuit Designs on Multiple Scales
100 µm
500 nm 500 nm
Huo, F et al. Science. 2008, 321, 1658.
Time Dependence
Feature Edge Length vs Dwell Time
Huo, F. et al. Science. 2008, 321, 1658.
Liao. et al. Small, 2010, 6, 1082.
Z-Piezo Dependence
Feature Size vs Z-Piezo Extension
Feature Size Control
Force Dependent Pattern Feature Edge Length vs Force
feature top
top
L L FNEL
Tip-Height Sensing: Force Dependence
bottom top
ZF NEL L
H
F1 < F2
Liao. et al. Small, 2010, 6, 1082.
Tilted PPL Array Z Height of the Tilted Pen Array
0( , , , ) sin( ) sin( ) x y x yZ N N Z DN DNθ: tilting angle to the y axis
φ: tilting angle to the x axis
M1, M2 and M3:
Motors holding the pen array θ = 0.07°
φ = 0.06 °
Liao. et al. Nano Lett. 2010, 10, 1335.
Leveling the Pen Array by Force
Experimental Ftotal vs θ and φ
• At the perfect leveling position, the total force
reaches its global maximum
• For each fixed θ, the force reaches its local
maximum when φ=0 and vice verse
• Around the perfect leveling position, the
gradient is very large
( , , , ) ( , , , ) bottom top
x y x y
EL LF N N Z N N
H
( , ) ( , , , ) x y
total x y
N N
F F N N
φ/ ° θ/ °
F total /
mN
F
tota
l / m
N
Calculated Ftotal vs θ and φ
Leveling the Pen Array by Force
Liao. et al. Nano Lett. 2010, 10, 1335.
θ = 0°
2.54 ± 0.05 mm
θ = –0.01°
4.68 ± 0.89 mm
θ = +0.01°
5.33 ± 1.03 mm
0o
–0.01o
+0.01o
Leveled Patterns
Liao. et al. Nano Lett. 2010, 10, 1335.
Multiplexed Protein Patterning by PPL
Inkjet print multiple
protein into inkwells
inkwells
Inkwells with different
fluorescent proteins
Pattern multiplexed
protein arrays
Multiplexed patterning
of protein arrays
Zheng, Z et al. Angew Chem. 2009, 48, 7626 .
Feature size control
Combinatorial Libraries Generated by
Tilting PPL Array
Printed Area
PPL array
substrate
High contact force
Low contact force
Feature width = 1.34 μm
Feature pitch = 2 μm
Feature width = 475 nm
Feature pitch = 2 μm
Large area patterns
Why PPL?
• Patterns over large areas for studying thousands to millions of cells
• Ability to produce combinatorial arrays with different feature sizes (micro to nanoscale)
• Ability to level the PPL array and produce homogeneous features over large areas
100 μm
CBFα1 actin DAPI
MSC Differentiation Studied by PPL-
Generated Combinatorial Arrays
Massively Parallel Hybrid Silicon
Pen Nanolithography
10 μm
1 mm
Ultra-High Resolution
High Throughput
Mask-free Nanofabrication
Easy Alignment
Z-piezo Glue
Soft backing layer
Si tip
100 μm
500 μm
Pen Tip Array
1 um
22 nm
Different light reflection
In contact with the surface
Before contact with the surface
Massively Parallel Hybrid Silicon
Pen Writing
Time Dependence
Feature Edge Length vs Dwell Time
Z-Piezo Dependence
Feature Size vs Z-Piezo Extension
Feature Size Control
5 μm
Z=12 μm
10 μm
8 μm
4 μm
6 μm
0 1 2 3 40
200
400
600
800
1000
1200
Do
t d
iam
ete
r (n
m)
Contact time (s1/2
)
4 6 8 10 120
200
400
600
800
1000
1200
Dia
me
ter
(nm
)
Z-piezo Extension (um)
5 μm
i ii
iii iv
i
ii
iii
iv
10 μm
Feature Size Resolution
Average Feature
Size = 42 nm
5 μm
5 μm 5 μm
Block Copolymer Assisted TBN
-10
10
30
50
0 2 4 6 8 10
100 nm
100 nm 90 °
5 µm
Distance (µm)
Heig
ht
(nm
)
5 µm
2 µm
Block Copolymer (BCP) Patterns
BCP Deposition (Height) BCP Deposition (Phase)
AFM Height Profile
Cai et al, submitted
Single Nanoparticles Formed by
Block Copolymer TBN
• The spatial resolution is controlled by the piezo-controlled tip position
• Fourier transform analysis confirms uniformity of the AuNP pattern
• Sub-10 nm single crystal Au NPs are formed by the BCP method
• TEM and Diffraction patterns confirm single crystal composition of the
nanostructures
TEM and Diffraction of AuNP SEM of AuNP Array
Cai et al, submitted
Nanoparticle Size Control
Cai et al, submitted
1 µm
Large-Scale Patterning
Au NPs on SiO2
Cai et al, submitted
Particle Size Consistency
Au NPs on SiO2
Cai et al, submitted
Growth Trajectories: Cryo-TEM Movie of
Ripening Process
2 nm
FOR OFFICIAL USE ONLY – Not Cleared for Open Release
Formation of Single
Nanoparticles Observed
-120 degrees C, ~ 1 min frame interval
FOR OFFICIAL USE ONLY – Not Cleared for Open Release
Two Mechanisms are Occurring
-120 degrees C, ~ 5 min frame interval
• Coalescence observed for particles closer than ~ 5 nm
• Ostwald ripening observed for particles further apart
Fabricating a Beam Pen Array
BPL array 200 nm Aperture 1 μm Aperture 2 μm Aperture
100 μm 2 μm 2 μm 20 μm
Beam Pen Lithography (BPL)
Huo et al, submitted
BPL Scheme Au dot arrays by BPL 10 x 10 dot array
Chicago Skyline Arbitrary patterns by BPL
Develop
Evaporation +
liftoff
Patterning
150 μm
100 μm
20 μm
Beam Pen Lithography (BPL)
Huo et al, submitted
Mask-Assisted BPL
• Drawbacks:
– Photo mask is needed
– Can not in-situ address the pens
Mask assisted BPL Patterns of “NU” with selected pens
Huo et al, submitted
Development of Molecular Printing Tools Parallel Printing
Serial Writing
Woodblock Printing (China ~200)
Printing Press (Gutenberg, 1439)
Movable Type (Bi Sheng, ~1041-1048)
μ-Contact Printing (Whitesides, 1993)
Quill Pen (~2000 BC)
Dip-Pen
Nanolithography (DPN) (Mirkin, 1999)
Ball-Point (Loud, 1888)
Polymer Pen
Lithography (PPL) (2008)
Beam Pen
Lithography (BPL) (2010)
Hard Tip, Soft Spring
Lithography (2010)
Scanning Probe Block
Copolymer Lithography (2010)
A Step Towards “Desktop Nanofabrication”:
Take Home Messages
• DPN and PPL are workhorse molecular printing research
tools, which allow researchers to rapidly prototype and
study molecule-based structures.
• The barrier to scanning probe parallelization is
crumbling; PPL, BPL, and SPBCL open the door for low
cost and rapid nanofabrication procedures.
• The techniques are poised to make the transition from
primarily research tools to high throughput synthesis
and fabrication tools, especially in the life sciences.
World Use of Dip Pen Nanolithography
Australia: Swinburne U. – Nicolau Canada: U.of Alberta – Buriak China: Chinese Acad. of Sci .(Lanzhou) – Li CIST – Hua Peking U. – J. Liu , Y Li. Chinese Acad. of Sci. (Shanghai )- Zhang Chinese Acad. of Sci.(Beijing) –Z. Liu Xi’an Jiaotong U. – Zhang, Liu Southwest U. – Tang Columbia: Servico Nacional de Aprendizaje (SENA) France: CNRS France – Joachim Germany: Inst. für NanoTechnologie, Forschungszentrum Karlsruhe– Fuchs Ludwig Inst.– Bein Max Planck Inst. – Bastiaen Great Britain: U. of Cambridge –Rayment Imperial College – Cass U. of Ulster U. of Strathclyde –Graham Hong Kong: Xu
India: CEERI – Kumar Jawaharlal Nehru Cen. for Adv. Sci. Research– Rao Indian Inst. Sci. – Brar Israel: Hebrew U. – Willner Italy: Politec. di Milano – Levi U. degli Studi di Milano Bicocca – Sassella
Japan: NAIST– Ushijima Nagoya U.– Ichimiya Korea: Samsung Electronics, Co. Seoul Nat. U. – Nam, S. Hong Pusan Nati. U. – Il Kim Sungkyunkwan U. – HJ Kim Korea U. –Ahn Yonsei U.–H. Jung Netherlands: U. of Twente– Reinhoudt, Velders Singapore: Nanyang Tech–Liu , Huo, Zhang , Boey, Huang Spain: Inst. Català– Maspoch, Garcia, Martinez Parc Cientific–Samitier Taiwan: Acad. Sinica–Tao Nat. Chiao Tung U.– Sheu Nat. Taiwan U.– Lin Schmidt Scientific
United States: Air Force Research – Naik, Stone Albany NanoTech – Kossow Brookhaven – Ocko Cal.Tech.– Collier Cal. State – Schwartz Corning Inc Science & Tech Duke U. – J. Lui, Chilkoti George Mason U. – Espina Georgia NanoFab – Lewis Harvard U. – Lieber Lawrence Berkeley – De Yoreo Loyola U. – Holz
MIT – Stellacci NASA Langley – Watkins Naval Research – Byers, Whitman, Sheehan N. Carolina State U. – Narayan Northwestern U.– Dravid, Liu, Mirkin, Wolinsky, Espinosa NYU – Braunschweig Ohio State U.– Lee Penn State U.– Weiss Portland State University- Yan, La Rosa Purdue U. – Ivanesivic Rensselaer Poly.– Nalamasu Sandia NL – Hsu Stanford U. – Bao Stevens IT – Libera Texas A & M – Banerjee, Batteas Texas Tech – Vaughn, Weeks Tufts U. – Kaplan
UMass Lowell - Mead UC Davis – G. Liu UCSB – Hu U. of Chicago – Mrkisch U. of Florida – Ren UIUC – C. Liu, U. of Maryland – Gomez U. of N. Carolina – Zauscher U. of Washington – Ginger Washington Tech Center – Allen
Mirkin Group
Acknowledgements
Funding
AFOSR, ARO DARPA (TBN Program),
HSARPA, NSF, ONR, NIH,
DOD NSSEF Fellowship
Collaborators Prof. Chang Liu (NU)
Prof. Harald Fuchs (Münster, Germany)
Dr. Steven Lenhert (Münster, Germany)
Prof. Mark Ratner (NU), Prof. Michael Bedzyk (NU)
Prof. Vinayak Dravid (NU), Dr. Morley Stone (WP AFRL)
Prof. Milan Mrksich (University of Chicago)
Prof. George Schatz (NU), Dr. Rajesh Naik (WP AFRL)
Prof. Hua Zhang (Nanyang Technical University, Singapore)
Joe Fragala (NanoInk)