NANONICS IMAGINGFOUNTAIN PEN
NanoLithography
Systems
The Next Evolution in AFM

Methods of Nanochemical Lithography
Fountain Pen NanoLithography
A. Lewis et al. Appl. Phys. Lett. 75, 2689 (1999)

Based on a NanoPipette• Any surface: flat or roughFPN controlled etching of chrome.
so far- Impossible with DPN• Wide variety of inks
• Reservoir for over a weekof writing with no dipping
needed• A NanoTool KitTM of probes
including probes for melting
inks on a surface

The Next Evolution in AFM

Methods of Nanochemical Lithography
Dip Pen NanoLithography
R. D. Piner et al. Science 283, 661 (1999)

Based on a meniscus
formation with a water layeron the surface to be written• Requires very flat surfaces• Very limited inks
• Only gold substrate• Highly limited systems• Highly limited probes

The Next Evolution in AFM

Nanonics Unique FPN Systems• Any solvent• Any Problem• Any view

– Organic– Aqueous– Etching– Above– Printing conducting– Belowpatterns– Both• Any surface– Gas deposition– True independent– Smooth surface– Protein chips
MultiProbe– Rough surface
operation– Hydrophobic– Any materialpolymer• On-line
surface: Silicon;
nanoparticles
spectroscopic
Glass; Metal– Circuit edit
characterization–Photoniccircuits• Any ink
– Fluorescence– Gold nanoparticles • Ultimate control– Raman
Voltage Controlled– Gases– Near-Field optical
Electrophoretic&– Proteins
Dielectrophoretic– Nanotubes
Deposition– RodsThe Next Evolution in AFM

Nanoparticle Deposition
Gold Nanoparticles in Methanol
Deposited on SiliconLine Width: ~100nm
Line Height: ~15nm

Registration of a gold nanoparticle line (100 nm wide & 15 nm high) to a gold line (250nm wide & 50 nm high) patterned by electron beam lithography
The Next Evolution in AFM

Nanonics Unique FPN Systems• Any solvent• Any Problem• Any view

– Organic– Aqueous– Etching– Above– Printing conducting– Below
patterns– Both• Any surface– Gas deposition– True independent– Smooth surface– Protein chips
MultiProbe– Rough surface
operation– Hydrophobic– Any material
polymer• On-line
surface: Silicon;
nanoparticles
spectroscopic
Glass; Metal– Circuit edit
characterization–Photoniccircuits• Any ink
– Fluorescence– Gold nanoparticles • Ultimate control– Raman
Voltage Controlled– Gases– Near-Field optical
Electrophoretic&– Proteins
Dielectrophoretic– Nanotubes
Deposition– RodsThe Next Evolution in AFM

FPN gold NanoLine- full view
SEM Image

AFM ImageSEM imaging of the FPN deposited gold showing conductivity of the line
The Next Evolution in AFM

Characterization of the FPN written
gold line
EDS measurementof the gold line:

I-V Characterization of thegold line without annealing,i.e. gold nanoparticle ink notmelted together
The line slope shows Ohmic
behavior with resistance of ~ 650ohms.
The Next Evolution in AFM

Nanonics Unique FPN Systems• Any solvent• Any Problem• Any view

– Organic– Aqueous– Etching– Above– Printing conducting– Belowpatterns– Both• Any surface– Gas deposition– True independent– Smooth surface– Protein chips
MultiProbe– Rough surface
operation– Hydrophobic– Any materialpolymer• On-line
surface: Silicon;
nanoparticles
spectroscopic
Glass; Metal– Circuit edit
characterization–Photoniccircuits• Any ink
– Fluorescence– Gold nanoparticles • Ultimate control– Raman
Voltage Controlled– Gases– Near-Field optical
Electrophoretic&– Proteins
Dielectrophoretic– Nanotubes
Deposition– RodsThe Next Evolution in AFM

Gas Phase Delivery & Nanochemistry
Only With FPN

The Next Evolution in AFM

Nanonics Unique FPN Systems• Any solvent• Any Problem• Any view

– Organic– Aqueous– Etching– Above– Printing conducting– Belowpatterns– Both• Any surface– Gas deposition– True independent– Smooth surface– Protein chips
MultiProbe– Rough surface
operation– Hydrophobic– Any materialpolymer• On-line
surface: Silicon;
nanoparticlesspectroscopic
Glass; Metal– Circuit edit
characterization–Photoniccircuits• Any ink
– Fluorescence– Gold nanoparticles • Ultimate control– Raman
Voltage Controlled– Gases– Near-Field optical
Electrophoretic&– Proteins
Dielectrophoretic– Nanotubes
Deposition– RodsThe Next Evolution in AFM

The Nanonics Multiprobe MultiView
FPN System

Only Nanonics has Independently
Controlled MultiProbes
The Next Evolution in AFM

The Nanonics Multiprobe MultiView
Full View FPN System

An upright microscope view of four probes approachingan opaque sample in close proximity.
Unique optical and multiprobe friendly probe structure
enables imaging all probes in NanoToolKitTM
The Next Evolution in AFM

NanoToolKitTM
Unique exposed tipoptically & multiprobe friendly probes
NanoOptical Light Source
Nanopipettes for:––Ionic Conductance
NanoFountain Pens for•–Generalprobe
properties:

MultiProbe Friendly

Liquid & Gas Delivery

NanoEvacuation

NanoHeaters combined withDifferential Scanning Calorimetry

Optically Friendly:

Plasmonic NanoProbes with Single
Gold NanoParticles• Non-Obscuring
Non-Interfering
Cantilevers

Glass Insulated Coaxial
NanoElectrical & Cantilevered
NanoElectrochemical Probes• Probe Tips
Exposed To The
Optical Axis

The Next Evolution in AFM

Nanonics FPN Systemversus DPN System
DPN System:
Restricted Viewblocked from above

Nanonics Full View FPN Systems:- All are accessible from above and beneathSingle Probe

Two Probe

Four Probe
The Next Evolution in AFM

Nanonics Unique FPN Systems• Any solvent• Any Problem• Any view

– Organic– Aqueous– Etching– Above– Printing conducting– Belowpatterns– Both• Any surface– Gas deposition– True independent– Smooth surface– Protein chipsMultiProbe– Rough surface
operation– Hydrophobic– Any material
polymer• On-line
surface: Silicon;
nanoparticles
spectroscopic
Glass; Metal– Circuit edit
characterization–Photoniccircuits• Any ink
– Fluorescence– Gold nanoparticles • Ultimate control– Raman
Voltage Controlled– Gases– Near-Field optical
Electrophoretic&– Proteins
Dielectrophoretic– Nanotubes
Deposition– RodsThe Next Evolution in AFM

MultiProbe Writing & Imaging
Protein Bovine Serum Albumin On Conventional
Protein Spotting Glass Substrates
Writing

Reading

Protein Spotting on standard Superoxide or Superaldehde proteinmacrospotting substrates.
- No need for protein modification as in DPN- Full protein activity for binding studies
The Next Evolution in AFM

Standard Macro Spottingof Proteins On Conventional
Protein Spotting Glass Substrates
from Telechem International•

G. MacBeath & S. L. Schreiber, Science 289,
1760 (2000)•Aldehyde slides were purchased from
TeleChem International (Cupertino, CA)
under the trade name SuperAldehyde orSuperepoxide Substrates•

Spotted using a GMS 417 Arrayer(Affymetrix, Santa Clara, CA) for Fig. 2,proteins were spotted using a split pinarrayer

The Next Evolution in AFM

NanoFountain Pen Protein Printing:Indpendent Comparison with Dip-Pen
Phillip Ball in Nature Materials'fountain pen' can have different
inks channelled into it
automatically, simply byconnecting it up to standard highperformance liquid
chromatography instrumentation.
This should make writing a multiprotein nanoarray much easierthan by using DPN, and without
the need for any complex pretreatment of the substrate.
The Next Evolution in AFM

Both FPN & DPN Have No Controlof the Writing in Contact
DPN Probe

FPN Probe With Its Reservoir& Inherent Writing Capabilites,
Multiprobe & Spectral
Transparency Advantages &Its Long Reach Into DeepTrenches

The Next Evolution in AFM

Both Dip Pen Lithography & Fountain
Pen Lithography Suffer From
A Lack Of Control
When The Probe Touch They Write.
Nanonics Offers
The Ultimate in Control With
Voltage Controlled Liquid Deposition orGas Phase Chemical NanoDelivery with
the Ultimate in Resolution
The Next Evolution in AFM

Now Nanonics Introduces
Voltage Control ofNanoChemical Deposition The
Ultimate in NanoChemical
Lithography

The Next Evolution in AFM

Protein Writing With Electrophoretic
Voltage ControlCounterelectrodeGold coatingon the pipetteexteriorElectrophoretic Control
The Next Evolution in AFM

The Ultimate in Writing Control
Voltage Controlled Deposition

The Next Evolution in AFM

A Variety of Voltage Control Protocols
For a Variety of Setups
Voltage between
back side & front side of pipette

Voltagethe surface
Voltagebetween
between& thefront
side of the pipettebackside& sample

Voltage as above but also between theback side of the pipette & the sample`
Positive pulse:
v1

v2

V3>V2>V1

v3

Negative pulse:
V1>V2>V3
The Next Evolution in AFM

Nanonics Unique FPN Systems• Any solvent• Any Problem• Any view

– Organic– Aqueous– Etching– Above– Printing conducting– Belowpatterns– Both• Any surface– Gas deposition– True independent– Smooth surface– Protein chips
MultiProbe– Rough surface
operation– Hydrophobic– Any materialpolymer• On-line
surface: Silicon;
nanoparticles
spectroscopic
Glass; Metal– Circuit edit
characterization–Photoniccircuits• Any ink
– Fluorescence– Gold nanoparticles • Ultimate control– Raman
Voltage Controlled– Gases– Near-Field optical
Electrophoretic&– Proteins
Dielectrophoretic– NanotubesDeposition– Rods
The Next Evolution in AFM

Combining Voltage Controlled NanoChemicalWriting With On-line Fluorescence & Raman

The Next Evolution in AFM

Transparent Integration ofNanonics FPN Systems
With High End Spectroscopic Systems
All MultiView
FPN Systems
CombineTransparently
with On-line
Spectral Analysis

MV 4000 MultiProbe Platform

MV 2000 Platform
The Next Evolution in AFM

Protein Writing With
Electrophoretic Voltage Control &Fluorescence Detection

The Next Evolution in AFM

Protein Deposition With Voltage
Controlled Electrophoretic Deposition

The Next Evolution in AFM

Nanonics Unique FPN Systems• Any solvent• Any Problem• Any view

– Organic– Aqueous– Etching– Above– Printing conducting– Belowpatterns– Both• Any surface– Gas deposition– True independent– Smooth surface– Protein chips
MultiProbe– Rough surface
operation– Hydrophobic– Any materialpolymer• On-line
surface: Silicon;
nanoparticles
spectroscopic
Glass; Metal– Circuit edit
characterization–Photoniccircuits• Any ink
– Fluorescence– Gold nanoparticles • Ultimate control– Raman
Voltage Controlled– Gases– Near-Field optical
Electrophoretic&– Proteins
Dielectrophoretic– NanotubesDeposition– Rods
The Next Evolution in AFM

AFM & SEM of Nanowriting of Gold
Nanoparticles in Methanol

140 nmThe Next Evolution in AFM

Electrophoretic Deposition ofSingle 1.4 nm Gold Nanoparticles
Height 1.4 nm
Reproducibility of + 0.2 nm. The
Reproducibility of the Supplied GoldColloids
2

Height in AFM defines colloid orquantum dot dimensions
Fountain Pen Aperture I.D.
20nm
O.D 40nm

Z[nm]

1.5

1

0.5

00

0.2

0.4

0.6

0.8

1X[µm]The Next Evolution in AFM

Nanonics Unique FPN Systems• Any solvent• Any Problem• Any view

– Organic– Aqueous– Etching– Above– Printing conducting– Belowpatterns– Both• Any surface– Gas deposition– True independent– Smooth surface– Protein chips
MultiProbe– Rough surface
operation– Hydrophobic– Any material
polymer• On-line
surface: Silicon;
nanoparticles
spectroscopic
Glass; Metal– Circuit edit
characterization–Photoniccircuits• Any ink
– Fluorescence– Gold nanoparticles • Ultimate control– Raman
Voltage Controlled– Gases– Near-Field optical
Electrophoretic&– Proteins
Dielectrophoretic– Nanotubes
Deposition– RodsThe Next Evolution in AFM

Voltage Controlled Dielectrophoretic
Deposition of Polymer Nanoparticles inHexane
6.85 nm

60 nm

400nm
-2.15 nm

NanoWriting Polymer Nanoparticles
The Next Evolution in AFM

Nanonics Unique FPN Systems• Any solvent• Any Problem• Any view

– Organic– Aqueous withsurfactant– Etching– Above– Printing conducting– Below
patterns– Both– Gas deposition– True independent• Any surface– Protein chips
MultiProbe– Smooth surface
operation– Hydrophobic– Rough surface
polymer• On-line– Any material
nanoparticles
spectroscopic
surface: Silicon;– Circuit edit
Glass; Metal
characterization– Photonic circuits– Fluorescence• Any ink
• Ultimate control– Raman– Gold nanoparticles
Voltage Controlled– Near-Field
Electrophoretic &– Gases
optical
Dielectrophoretic– Proteins
Deposition– Nanotubes– RodsThe Next Evolution in AFM

Carbon NanoTube NanoDielectrophoretic
NanoWriting with Surfactant••

The ink: CNT with surfactants in water solution.
CNT dimension : diameter of 0.7-1.4 nm
Length of 1-1.5 µm.

AFM image of deposited Carbon Nanotubes

The Next Evolution in AFM

But is the written pattern reallycarbon nanotubes?
Raman can tell us!

The Next Evolution in AFM

Combining Voltage Controlled NanoChemicalWriting With On-line Raman

The Next Evolution in AFM

Raman Spectroscopy Insures
The Chemical Character of the Lines••

The ink: CNT with surfactants in water solution.
CNT dimension : diameter of 0.7-1.4 nm
Length of 1-1.5 µm.
AFM image of deposited Carbon Nanotubes

Raman spectrum from the Carbon
Nanotubes lines
1553

40

The Next Evolution in AFM

Raman Polarization Analysis FurtherShows Aligned Carbon Nanotubes
12001100
10009008007006005004003002001000Orientation F ver
Orientation F hor

On-line Raman
Orientation G hor
polarization analysis
show orientation due
9001000 1100 1200 1300 1400 1500 1600
Raman shift / cm-1
to the dielectrophoretic
controlled voltage
Polarisation dependence of changing
writing process that
Sample orientation
also has the potential
for conducting and3.5
semiconducting tube
3separation
2.5
Orientation G ver

Ratio of corrected peakheights of vertically polarised
light response over horizontally
polarised light response

countsRaman spectra (uncorrected)

21.5
10.5
00306090120

150

180

Angle of nanotube line from vertical / degrees

The Next Evolution in AFM

SEM of Deposited & Registered
Carbon NanoTube

The Next Evolution in AFM

Nanonics Unique FPN Systems• Any solvent• Any Problem• Any view

– Organic– Aqueous– Etching– Above– Printing conducting– Below
patterns– Both• Any surface– Gas deposition– True independent– Smooth surface– Protein chips
MultiProbe– Rough surface
operation– Hydrophobic– Any material
polymer• On-line
surface: Silicon;
nanoparticles
spectroscopic
Glass; Metal– Circuit edit
characterization–Photoniccircuits• Any ink– Fluorescence– Gold nanoparticles • Ultimate control– Raman
Voltage Controlled– Gases– Near-Field optical
Electrophoretic&– Proteins
Dielectrophoretic– Nanotubes
Deposition– RodsThe Next Evolution in AFM

Problems With Complicated Surface
Structure Such As Circuit Edit Can Be
Attacked Only by FPN
After

BeforeZ = - 2.2 m

Z = - 1.4 m

2 m DeepControlled filling of 0.5 m X 0.5 m trenches in silicon withpure gold nanoparticles in a circuit edit application
The Next Evolution in AFM

BeforeAfter2.68 ｵm

0.00 ｵm

1.73 ｵm

1.40.00 ｵm

1.221Z[µm]

Z[µm]

1.5
10.8
0.6
0.4

0.5
00.2
000.2 0.4 0.6 0.8 1

X[µm]1.2 1.4 1.6

00.2 0.4 0.6 0.8

11.2 1.4 1.6

X[µm]

The Next Evolution in AFM

Immediately After

One Week After

1.86 ｵm0.00 ｵm

1.41.2

1.2

110.8

Z[µm]

Z[µm]

1.4

0.6

0.8
0.6

0.4

0.4

0.2

0.2

0000.2 0.4 0.6 0.8

X[µm]11.2 1.4 1.6

00.2 0.4 0.6 0.8

11.2 1.4 1.6

X[µm]

The Next Evolution in AFM

Nanonics Unique FPN Systems• Any solvent• Any Problem• Any view

– Organic– Aqueous– Etching– Above– Printing conducting– Belowpatterns– Both• Any surface– Gas deposition– True independent– Smooth surface– Protein chips
MultiProbe– Rough surface
operation– Hydrophobic– Any materialpolymer• On-line
surface: Silicon;
nanoparticles
spectroscopic
Glass; Metal– Circuit edit
characterization–Photoniccircuits• Any ink
– Fluorescence– Gold nanoparticles • Ultimate control– Raman
Voltage Controlled– Gases– Near-Field optical
Electrophoretic&– Proteins
Dielectrophoretic– Nanotubes
Deposition &– RodsRegistration
The Next Evolution in AFM

Ultimate In Registration & Deposition
With Voltage Controlled NanoPrinting
for Controlled Short Circuiting

The Next Evolution in AFM

Nanonics Unique FPN Systems• Any solvent• Any Problem• Any view

– Organic– Aqueous– Etching– Above– Printing conducting– Belowpatterns– Both• Any surface– Gas deposition– True independent– Smooth surface– Protein chips
MultiProbe– Rough surface
operation– Hydrophobic– Any materialpolymer• On-line
surface: Silicon;
nanoparticles
spectroscopic
Glass; Metal– Circuit edit
characterization–Photoniccircuits• Any ink
– Fluorescence– Gold nanoparticles • Ultimate control– Raman
Voltage Controlled– Gases– Near-Field optical
Electrophoretic&– Proteins
Dielectrophoretic– Nanotubes
Deposition &– Rods
Registration
The Next Evolution in AFM

Selective Protein Deposition in a Single
Hole of a 1.5 micron Photonic Band Gap

The Next Evolution in AFM

With Near-field Optical Characterization
AFM

Near-Field opticalwith injectedmaterial in PBG

Highly flexible platform thatallows light injection fromabove, below & even fromthe sides for Nanochemical
Deposition and Optical
Characterization

The Next Evolution in AFM

Nanonics Unique FPN Systems• Any solvent• Any Problem• Any view

– Organic– Aqueous– Etching– Above– Printing conducting– Below
patterns– Both• Any surface– Gas deposition– True independent– Smooth surface– Protein chips
MultiProbe– Rough surface
operation– Hydrophobic– Any material
polymer• On-line
surface: Silicon;
nanoparticles
spectroscopic
Glass; Metal– Circuit edit
characterization–Photoniccircuits• Any ink– Fluorescence– Gold nanoparticles • Ultimate control– Raman
Voltage Controlled– Gases– Near-Field optical
Electrophoretic&– Proteins
Dielectrophoretic– Nanotubes
Deposition &– RodsRegistration
The Next Evolution in AFM

Selective Fluorescent Protein
Deposition in a Photonic Band Gap

Fluorescence
Image BSA in
Photonic Band
Gap With Center
Surround Control

The Next Evolution in AFM

ENTER A NEW WORLD OF
NANOCHEMICAL LITHOGRAPHY
withNanonics Exclusive FPN & ACCE
Atomic Force Controlled
Electrophoretic Depositon
Technology

The Next Evolution in AFM