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Erik DUJARDIN SPM-based surface nanopatterning 1 SPM-based surface nanopatterning Microscopies en champ proche pour la nanostructuration de surfaces Erik DUJARDIN NanoSciences Group CEMES -CNRS UPR 8011 B.P. 94347 - 29 rue J. Marvig 7RXORXVH ± )5$1&( [email protected]
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Page 1: SPM-based surface nanopatterning · PDF fileElectrolysis of loaded solutions ... for thiol or silane chemistry ... Erik DUJARDIN SPM-based surface nanopatterning 34

Erik DUJARDIN SPM-based surface nanopatterning 1

SPM-based surface nanopatterning

Microscopies en champ prochepour la nanostructuration de surfaces

Erik DUJARDINNanoSciences GroupCEMES -CNRS UPR 8011B.P. 94347 - 29 rue J. Marvig������7RXORXVH�± )5$1&(

[email protected]

pdfMachine by Broadgun Software - a great PDF writer! - a great PDF creator! - http://www.pdfmachine.com http://www.broadgun.com

Page 2: SPM-based surface nanopatterning · PDF fileElectrolysis of loaded solutions ... for thiol or silane chemistry ... Erik DUJARDIN SPM-based surface nanopatterning 34

Erik DUJARDIN SPM-based surface nanopatterning 2

IntroductionIntroduction DipDip--PenPen IonscopeIonscope Bioforce/BioplumeBioforce/Bioplume NADISNADIS OutlookOutlook

IntroductionIntroductionIntroduction

Scanning Probe Microscopies

1982 : Scanning Tunneling Microscope(STM)

H. Rohrer and G. Binnig�,%0�=�ULFK�

G. Binnig, H. Rohrer, Ch. Gerber, E. Weibel, Phys. Rev. Lett. 50, 120 (1982)

1986 : Atomic Force Microscope(AFM)

G. Binnig, C. F. Quate�,%0�=�ULFK��8QL��6WDQIRUG�

G. Binnig US Pat. RE 33 387 (1985);G. Binnig, C.F. Quate, Ch. Gerber, Phys. Rev. Lett. 56, 930 (1986)

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Erik DUJARDIN SPM-based surface nanopatterning 3

IntroductionIntroduction DipDip--PenPen IonscopeIonscope Bioforce/BioplumeBioforce/Bioplume NADISNADIS OutlookOutlook

IntroductionIntroductionIntroduction

Manipulating matter with SPM

1990s : Scanning Tunneling Microscope(STM)

D. Eigler, J. Gimzewzky�,%0�=�ULFK�

D.M. Eigler, E.K. Schweizer. Nature 344, 524-526 (1990). M.F. Crommie, C.P. Lutz, D.M. Eigler. Science 262, 218-220 (1993).M. T. Cuberes, R. R. Schlittler, J. K. Gimzewski, App. Phys. Lett. 69, 3016 (1996).

1995 : Atomic Force Microscope

D.M. Scheffer (Purdue Uni.)L. Samuelson (Uni. Lund)

D. M. Schaefer, et al., Appl. Phys. Lett. 66, 1012 (1995).T. Junno, K. Deppert, L. Montelius, L. Samuelson, Appl. Phys. Lett. 66, 3627 (1995).

Xe on Nickel (110)C60 on Copper (111)

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Erik DUJARDIN SPM-based surface nanopatterning 4

IntroductionIntroduction DipDip--PenPen IonscopeIonscope Bioforce/BioplumeBioforce/Bioplume NADISNADIS OutlookOutlookIntroductionIntroduction DipDip--PenPen IonscopeIonscope Bioforce/BioplumeBioforce/Bioplume NADISNADIS OutlookOutlook

IntroductionIntroductionIntroduction

Surface patterning

Texture and topography

Surface energy

Chemical composition

«

Super-hydrophobicity

Cell confinement

Localized growth

Optical properties

«

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Erik DUJARDIN SPM-based surface nanopatterning 5

IntroductionIntroduction DipDip--PenPen IonscopeIonscope Bioforce/BioplumeBioforce/Bioplume NADISNADIS OutlookOutlook

IntroductionIntroductionIntroduction

Lithography techniques

Sensitive layer deposition

Pattern writing

Pattern transfer

«

Generic and parallel

Industrial process

Resolution

Costly

No localized patterning

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Erik DUJARDIN SPM-based surface nanopatterning 6

630�EDVHG�/LWKRJUDSK\�7HFKQLTXHV�������� «�

STM lithography

Local exposure to electric pulses.Current-induced heating, melting.Electrochemical reaction at surface.

AFM oxidation

Local exposure to electric bias.Mainly oxide growth induced in water.Any other redox reaction is possible.

AFM indentation

Tip is pressed into materialMechanical modification of surface

IntroductionIntroduction DipDip--PenPen IonscopeIonscope Bioforce/BioplumeBioforce/Bioplume NADISNADIS OutlookOutlook

IntroductionIntroductionIntroduction

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Erik DUJARDIN SPM-based surface nanopatterning 7

IntroductionIntroduction DipDip--PenPen IonscopeIonscope Bioforce/BioplumeBioforce/Bioplume NADISNADIS OutlookOutlook

Dip-Pen Nanolithography

Ionscope lithography

Bioforce/Bioplume systems

NADIS deposition system

Parallel SPM nanopatterning

Outlook

OverviewOverviewOverview

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Erik DUJARDIN SPM-based surface nanopatterning 8

IntroductionIntroduction DipDip--PenPen IonscopeIonscope Bioforce/BioplumeBioforce/Bioplume NADISNADIS OutlookOutlook

Dip-Pen Nanolithography (DPN) - 1999DipDip--Pen Nanolithography (DPN) Pen Nanolithography (DPN) -- 19991999

Principle and initial reports

An AFM tip is dipped into a solution and dried.(ex.: saturated 1-octadecanethiol inacetonitrile; 1 min)

Writing is obtained by rastering the inked tip ona gold substrate.

Piner, R. D.; Zhu, J.; Xu, F.; Hong, S.; Mirkin, C. A. Science 1999, 283, 661.S. Hong, J. Zhu, and C. A. Mirkin, Langmuir 1999, 15, 7897.Hong, S.; Zhu, J.; Mirkin, C. A. Science 1999, 286, 523.

1Hz, 10min, 39%RH 9Hz, 0.56s, 39%RH

1Hz, 5min, 3 m1Hz, 5min, 3 1Hz, 5min, 3 mm 1Hz, 1.5min, 3 m1Hz, 1.5min, 3 1Hz, 1.5min, 3 mm

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IntroductionIntroduction DipDip--PenPen IonscopeIonscope Bioforce/BioplumeBioforce/Bioplume NADISNADIS OutlookOutlook

Ink diffusion on substrateInk diffusion on substrateInk diffusion on substrate

Underlying principle: molecular diffusion

Feature size depends on moleculardiffusion from the tip onto the substrate.

A = r2 = C. t

C depends on:- the substrate smoothness

- the ink diffusion coefficient

- the ink solvent

- the relative humidity

C18-SH HS-C15-CO2H (MHA)

2 4 16 mn10 20 40 s

45%RH 35%RH

MHA in methanol

4 8 16 20s

MHA in 1-butanol MHA in 1-octanol Image size : 7.25 m

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IntroductionIntroduction DipDip--PenPen IonscopeIonscope Bioforce/BioplumeBioforce/Bioplume NADISNADIS OutlookOutlook

Applications (1)Applications (1)Applications (1)

Magnetic nanostructures

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Erik DUJARDIN SPM-based surface nanopatterning 11

IntroductionIntroduction DipDip--PenPen IonscopeIonscope Bioforce/BioplumeBioforce/Bioplume NADISNADIS OutlookOutlook

Applications (2)Applications (2)Applications (2)

DNA arrays

L. M. Demers, D. S. Ginger, S.-J. Park,Z. Li, S.-W. Chung, C. A. Mirkin,Science 296, 1836 (2002);

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IntroductionIntroduction DipDip--PenPen IonscopeIonscope Bioforce/BioplumeBioforce/Bioplume NADISNADIS OutlookOutlook

Applications (3)Applications (3)Applications (3)

Antigene detection

Lee, K. B., Kim, E. Y., Mirkin, C. A. & Wolinsky, S. M.,Nano Lett. 4, ����±������������

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IntroductionIntroduction DipDip--PenPen IonscopeIonscope Bioforce/BioplumeBioforce/Bioplume NADISNADIS OutlookOutlook

Inking the DPN tipsInking the DPN tipsInking the DPN tips

Automated inking from single/multiple microwells

DPN requires regular tip refilling

Standard solution : ink wells with automated motion

Drawback: dead time during refilling

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IntroductionIntroduction DipDip--PenPen IonscopeIonscope Bioforce/BioplumeBioforce/Bioplume NADISNADIS OutlookOutlook

Integrated fluidicsIntegrated fluidicsIntegrated fluidics

On-chip liquid reservoir and microcapillaries

Next generation of DPN tips will have integrated fluidics

S Deladi, et al., J. Micromech. Microeng. 15 ����������±���

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IntroductionIntroduction DipDip--PenPen IonscopeIonscope Bioforce/BioplumeBioforce/Bioplume NADISNADIS OutlookOutlook

Nano-fountain penNanoNano--fountain penfountain pen

On-chip liquid reservoir and microcapillaries

Next generation of DPN tips will have integrated fluidics

H.D. Espinosa, Small 2005, 1, 632

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Dip-Pen Nanolithography

Ionscope lithography

Bioforce/Bioplume systems

NADIS deposition system

Parallel SPM nanopatterning

Outlook

IntroductionIntroduction DipDip--PenPen IonscopeIonscope Bioforce/BioplumeBioforce/Bioplume NADISNADIS OutlookOutlook

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NanoPipette - imagingNanoPipetteNanoPipette -- imagingimaging

L. Ying et al., Phys. Chem. Chem. Phys., 2005, 7, 2859

IntroductionIntroduction DipDip--PenPen IonscopeIonscope Bioforce/BioplumeBioforce/Bioplume NADISNADIS OutlookOutlook

Scanning Ion Conductance Microscopy

Derived from Scanning Electrochemical Microscopy.A glass pipette (100-200 nm diameter) is scanned above the substrate.Distance modulation improves substantially the control of the sample-pipette spacing

If counter-electrode is in a cell, SCIM enablesmapping of K+ ion channels with a lateral resolutionof 400 nm.

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2-step spotting of green Alexa 488 and red Alexa 647

2-step spotting of rabbit IgG (green) and anti-rabbit IgG (red)

IntroductionIntroduction DipDip--PenPen IonscopeIonscope Bioforce/BioplumeBioforce/Bioplume NADISNADIS OutlookOutlook

A. Bruckbauer et al., J. Am. Chem. Soc., 2003, 125, 9834

Controlled delivery of solutes by pulsing the nanopipette

The inner volume of the pipette is used as a reservoir.

Solutes are specifically delivered by choosing the sign and amplitude of the applied voltage pulse.

1DQR3LSHWWH ± SDWWHUQLQJ�LQ�OLTXLGVNanoPipetteNanoPipette ±± patterning in liquidspatterning in liquids

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5 m 3 m

IntroductionIntroduction DipDip--PenPen IonscopeIonscope Bioforce/BioplumeBioforce/Bioplume NADISNADIS OutlookOutlook

Nano Lett., 6 (2), 252 -257, 2006

Controlled delivery of solution droplets

Aqueous solution in the pipette is deposited on a substrate submergedin an organic solvent upon pulsing.

,RQVFRSH ± IHPWROLWHU GURSOHW�SURGXFWLRQIonscopeIonscope ±± femtoliterfemtoliter droplet productiondroplet production

30V, 0.3s4.9 m

30V, 0.05s620 nm

Alexa 647 spots deliveredfrom compartment 1 in 40s

Alexa 488 spots deliveredfrom compartment 2 in 40s

with reversed polarity

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IntroductionIntroduction DipDip--PenPen IonscopeIonscope Bioforce/BioplumeBioforce/Bioplume NADISNADIS OutlookOutlook

D. Klenermann et al. Angew. Chem. Int. Ed. 2005, 44, 6854

Delivering micrometric droplets

1 - Upon approaching a moderately hydrophilicsurface a liquid meniscus is formed.

2 - Modulation of the pipette-substratedistance ensures the surface tracking

3 - An applied voltage between the twocompartments induces the molecular flow

Delivering micrometric droplets

Delivered amount isproportional to V

Spot size increaseslinearly with time:Diffusion mechanism

,RQVFRSH ± QDQRSDWWHUQLQJ RI�GU\�VXEVWUDWHVIonscopeIonscope ±± nanopatterningnanopatterning of dry substratesof dry substrates

t = 10s

V = 2V

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Double-barreled pipette-print75x61 m2, 1- m pxlGreen rhodamine - DNAAlexa-647 red - DNAPrinting time : 35 min

IntroductionIntroduction DipDip--PenPen IonscopeIonscope Bioforce/BioplumeBioforce/Bioplume NADISNADIS OutlookOutlook

D. Klenermann et al., Angew. Chem. Int. Ed. 2005, 44, 6854

Multi-adsorbate surface nanopatterning

When the 2 compartments contain 2 charged dyes, these can be selectively depositedby reversing the applied voltage: DNA migrates out of the negatively charged compartment.

,RQVFRSH ± QDQRSDWWHUQLQJ RI�GU\�VXEVWUDWHVIonscopeIonscope ±± nanopatterningnanopatterning of dry substratesof dry substrates

Photoshop image75x61pxlGreen and Red channels only

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Dip-Pen Nanolithography

Ionscope lithography

Bioforce/Bioplume systems

NADIS deposition system

Parallel SPM nanopatterning

Outlook

IntroductionIntroduction DipDip--PenPen IonscopeIonscope Bioforce/BioplumeBioforce/Bioplume NADISNADIS OutlookOutlook

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IntroductionIntroduction DipDip--PenPen IonscopeIonscope Bioforce/BioplumeBioforce/Bioplume NADISNADIS OutlookOutlook

NanoEnabler and Bioplume micro-spottersNanoEnablerNanoEnabler and and BioplumeBioplume micromicro--spottersspotters

Quill-type spotters

Miniature fountain pen

Passive or active loading

Spot size : 1-100 m

Parallel spotting (up to 30)

Automation

Biological applications (Affimetrix)http://www.bioforcenano.com/

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IntroductionIntroduction DipDip--PenPen IonscopeIonscope Bioforce/BioplumeBioforce/Bioplume NADISNADIS OutlookOutlook

Bioplume micro-spotterBioplumeBioplume micromicro--spotterspotter

Structure of Bioplume quill

)

T. Leichle, et al., Nanotechnology, 16, 525 (2005)

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IntroductionIntroduction DipDip--PenPen IonscopeIonscope Bioforce/BioplumeBioforce/Bioplume NADISNADIS OutlookOutlook

Bioplume micro-spotterBioplumeBioplume micromicro--spotterspotter

Multicantilever arrays Capillary or electroactive loading

T. Leichle et al., Sensors Actuators A, 132, 590 (2006)

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Fluorophores, biomolecules and polymers

Colloids

500 nm PS beads in DMSO

IntroductionIntroduction DipDip--PenPen IonscopeIonscope Bioforce/BioplumeBioforce/Bioplume NADISNADIS OutlookOutlook

Solution and suspension patterningSolution and suspension patterningSolution and suspension patterning

A. Valsesia, et al., Small, 2, 1444, (2006)

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IntroductionIntroduction DipDip--PenPen IonscopeIonscope Bioforce/BioplumeBioforce/Bioplume NADISNADIS OutlookOutlook

Direct surface nanostructuringDirect surface Direct surface nanostructuringnanostructuring

Electrolysis of loaded solutions

- Pyrrole and DNA-functionalized pyrrole polymerizationfor biochip applications:

- Copper(II) reduction into 20 m disks

T. Leichle et al., Appl. Phys. Lett., 88, 254108 (2006)

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S. Arscott, D. Troadec, Nanotechnology 16 (2005) 2295

Saya D., et al., J. Micromech. Microeng., 17, N1-N5 (2007)

Towards attoliter droplet delivery with nano-quill

Two recent approaches to reduce the deposition area at the quill apex.

IntroductionIntroduction DipDip--PenPen IonscopeIonscope Bioforce/BioplumeBioforce/Bioplume NADISNADIS OutlookOutlook

BioplumeBioplumeBioplume

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Micron scale patterning

Pin & Ring method (DNA Chip).

Ink Jet

BioPlume

Nanoscale patterningDip Pen Lithography

+ Versatile techniques

-- � a����WR������P

+ � a�WHQV�RI��QP

-- Limited to diffusivemolecules

-- No reservoir

Piner et al., Science 1999Hong, Mirkin, Science 2000

Surface patterning methodsSurface patterning methodsSurface patterning methods

IntroductionIntroduction DipDip--PenPen IonscopeIonscope Bioforce/BioplumeBioforce/Bioplume NADISNADIS OutlookOutlook

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Dip-Pen Nanolithography

Ionscope lithography

Bioforce/Bioplume systems

NADIS deposition system

Parallel SPM nanopatterning

Outlook

IntroductionIntroduction DipDip--PenPen IonscopeIonscope Bioforce/BioplumeBioforce/Bioplume NADISNADIS OutlookOutlook

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Delivery of sub-100nm liquid droplets on surfaces

- Which parameters govern the droplet size?- What are the liquid transfer mechanisms?- Can a droplet be deposited on a nanostructure?

AFM tip description

- Rectangular silicon nitride cantilevers

- Double-sided gold coating

- Spring constant ~ N/m

- Hollow pyramidal tips

IntroductionIntroduction DipDip--PenPen IonscopeIonscope Bioforce/BioplumeBioforce/Bioplume NADISNADIS OutlookOutlook

NAno-DISpensing system (NADIS)NAnoNAno--DISpensingDISpensing system (NADIS)system (NADIS)

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Microfabricated NADIS tips with > 1 m apertures

On-chip liquid reservoir

20 m

HydrophilicSi3N4 loading area

HydrophobicAu-coatedcantilever

A. Meister et al., Appl. Phys. Lett.85, 6260 (2004)

20 mLiquidreservoir

IntroductionIntroduction DipDip--PenPen IonscopeIonscope Bioforce/BioplumeBioforce/Bioplume NADISNADIS OutlookOutlook

Microfabricated NADIS tipsMicrofabricated NADIS tipsMicrofabricated NADIS tips

A. Meister et al. Microelectron. Eng. 67-68, 644 (2003).

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1 2

100 nm

500 nm251 nm

35 nm100 nm

Two-step milling for positioning sub-100 nm aperture at AFM tip apexThinning from top side.Drilling from tip side yields smaller NADIS (record size: 35 nm)

NADIS tip modification by FIB and surface functionalization

Patterned Au / Si3N4 surfacefor thiol or silane chemistry

Thiol chemistry on nonModified Au-coated tips

IntroductionIntroduction DipDip--PenPen IonscopeIonscope Bioforce/BioplumeBioforce/Bioplume NADISNADIS OutlookOutlook

FIB milling of NADIS tipsFIB milling of NADIS tipsFIB milling of NADIS tips

$��3��)DQJ��(��'XMDUGLQ��7��2QGDUoXKXNanoLett., 6, 2368 (2006)

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Force curve are used to monitor individual depositionDeposition is performed at any desired location.Realtime force curve is recorded

Other parameters:- Contact time- Number of contacts- Contact force- Retraction speed

h1: vertical distance between snap-in height and substrate surface, i.e. indication of droplet size.

a b c d e

IntroductionIntroduction DipDip--PenPen IonscopeIonscope Bioforce/BioplumeBioforce/Bioplume NADISNADIS OutlookOutlook

Femto- (10-15) to zeptoliter (10-21) droplets depositionFemtoFemto-- (10(10--1515) to ) to zeptoliterzeptoliter (10(10--2121) droplets deposition) droplets deposition

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� 2Q�SHUIOXRULQDWHG 6L22

( adv �������

� 2Q�DPLQR�IXQFWLRQDOL]HG 6L22

( adv ������ ���P

IntroductionIntroduction DipDip--PenPen IonscopeIonscope Bioforce/BioplumeBioforce/Bioplume NADISNADIS OutlookOutlook

Surface energy of the substrateSurface energy of the substrateSurface energy of the substrate

With hydrophilic tips and substrates of decreasing surface energyUntreated Au coated tip. Aperture diameter : 400 nm

���P

� 2Q�K\GURSKLOLF 6L22

( �����

A. P. Fang, E. DujaUGLQ��7��2QGDUoXKX��1DQR/HWW�����������������

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70 nm * 120 nm

35 nm

870nm

a� a�����QP

500nm

� a����QP

With hydrophobic tips and hydrophilic substratesGas phase treatment of tips with dodecanethiol.

IntroductionIntroduction DipDip--PenPen IonscopeIonscope Bioforce/BioplumeBioforce/Bioplume NADISNADIS OutlookOutlook

Aperture size and spot diameterAperture size and spot diameterAperture size and spot diameter

6SRW � a���[�+ROH �

A. P. Fang, E. DujaUGLQ��7��2QGDUoXKX��1DQR/HWW�����������������

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800 nmNo Au coating800 nm800 nmNo Au coatingNo Au coating � a�����QP

�����P�����P

Spot diameter ~ Size of hydrophilic area

IntroductionIntroduction DipDip--PenPen IonscopeIonscope Bioforce/BioplumeBioforce/Bioplume NADISNADIS OutlookOutlook

NADIS tip surface engineeringNADIS tip surface engineeringNADIS tip surface engineering

Mixed hydrophobic/philic tips prepared by FIBThe gold coating is removed exposing a mixed Si3N4 / Au surface.

Functionalization can be selectively done on Si3N4 (silanes) or Au (thiols)

controlled pinning of the triple line.

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Affymetrix NanoEnabler (Bioforce) NADIS

10 m500 m

IntroductionIntroduction DipDip--PenPen IonscopeIonscope Bioforce/BioplumeBioforce/Bioplume NADISNADIS OutlookOutlook

Performance comparisonPerformance comparisonPerformance comparison

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Erik DUJARDIN SPM-based surface nanopatterning 39

IntroductionIntroduction DipDip--PenPen IonscopeIonscope Bioforce/BioplumeBioforce/Bioplume NADISNADIS OutlookOutlook

Force curvesForce curvesForce curves

A. P. Fang, E. DujaUGLQ��7��2QGDUoXKX��1DQR/HWW�����������������

A means for real-time monitoringRetraction curve is a signature of liquid transfer regime (Constant P or V)

Liquid transfer dynamics

Liquid transfer mechanismand realtime control

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0 5 10 15 200

200

400

600

800

1000

1200

1400

t (s)

IntroductionIntroduction DipDip--PenPen IonscopeIonscope Bioforce/BioplumeBioforce/Bioplume NADISNADIS OutlookOutlook

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Dynamics of the droplet growthDynamics of the droplet growthDynamics of the droplet growth

Time evolution of the transferred volumeV(t) is derived from h1(t) assuming a macroscopic contact angle.

Amino-functionalized substrate.

Femtoliter regime (10-15 L)Hydrophilic tip

Aperture 400 nm

Attoliter regime (10-18 L)Hydrophobic tip

Aperture 200 nm

Non diffusiveDynamics

Dip Pen Nanolithography

No dynamics

Equilibrium at first contact

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-70

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10

20

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z (nm)

Hydrophilic tip

Hydrophobic tip

Smallaperture

Profile of retraction force curves Liquid transfer mechanism

Correlation force curve shape - drop size Realtime monitoring of deposit

IntroductionIntroduction DipDip--PenPen IonscopeIonscope Bioforce/BioplumeBioforce/Bioplume NADISNADIS OutlookOutlook

Interpretation of retraction force curvesInterpretation of retraction force curvesInterpretation of retraction force curves

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Surface EvolverEnergy minimization for given boundary conditions or fixed parameters.

A modelization toolA A modelizationmodelization tooltool

� Surface shape� Energy� Pressure� Volume� Force

Pressure or volume

Radii or contact angles

IntroductionIntroduction DipDip--PenPen IonscopeIonscope Bioforce/BioplumeBioforce/Bioplume NADISNADIS OutlookOutlook

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IntroductionIntroduction DipDip--PenPen IonscopeIonscope Bioforce/BioplumeBioforce/Bioplume NADISNADIS OutlookOutlook

-80

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z (nm)

ExpCalc

2.Rsurf = 400 nm, 2.Rtip = 300 nm

P = 1.4 104 Pa

Fexp/Fcalc = 0.53 Fexp/Fcalc = 0.53

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Calc

2.Rsurf = 2.Rtip = 37.5 nm

V = 0.4 aL

Hydrophilic NADIS tipsHydrophilic NADIS tipsHydrophilic NADIS tips

Large apertures (400 nm)Constant pressureDefined by reservoir curvature

Small apertures (35 nm)Constant volumeNo flow through aperture during retraction

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-7

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0

0 0,5 1 1,5 2 2,5 3

z /Rtip

Rsurf = 1

Rsurf = 1,2

Rsurf = 1,5

Rsurf = 2

Rsurf = 2,2

Rsurf = 2,5

Rsurf = 3

Rsurf = 4

Rsurf = 5

Rsurf = 0,5

z / Rtip

Rsurf

IntroductionIntroduction DipDip--PenPen IonscopeIonscope Bioforce/BioplumeBioforce/Bioplume NADISNADIS OutlookOutlook

Correlating force curve and droplet sizeCorrelating force curve and droplet sizeCorrelating force curve and droplet size

Rtip = 1, varying Rsurf

Assumption : hydrophilic tip

2.RtipZrupt

0

0,5

1

1,5

2

2,5

3

0 0,5 1 1,5 2 2,5 3

Rsurf/RtipRsurf / RtipA. P. Fang, V. Orfila, E. Dujardin,7��2QGDUoXKX��LQ�SUHSDUDWLRQ

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Experimental assessment of the model

Rtip = 250 nm

Correlating force curve and droplet sizeCorrelating force curve and droplet sizeCorrelating force curve and droplet size

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����P

Rsurf

IntroductionIntroduction DipDip--PenPen IonscopeIonscope Bioforce/BioplumeBioforce/Bioplume NADISNADIS OutlookOutlook

0

0,5

1

1,5

2

2,5

3

0 0,5 1 1,5 2 2,5 3

Rsurf/Rtip

Rtip = 250 nm

Rsurf / Rtip

Zrupt

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Direct correlationbetween force curveand deposit size

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IntroductionIntroduction DipDip--PenPen IonscopeIonscope Bioforce/BioplumeBioforce/Bioplume NADISNADIS OutlookOutlook

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Experimental assessment of the model

Large aperture (400 nm) Constant pressure

Hydrophobic tip Contact line moves while withdrawing

Hydrophobic NADIS tipsHydrophobic NADIS tipsHydrophobic NADIS tips

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expcalc

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IntroductionIntroduction DipDip--PenPen IonscopeIonscope Bioforce/BioplumeBioforce/Bioplume NADISNADIS OutlookOutlook

Nano-positioning droplets on prepatterned surfacesNanoNano--positioning droplets on positioning droplets on prepatternedprepatterned surfacessurfaces

Double AFM tip set-up

Veeco Dimension AFM is modified with a closed-loop nanopositioning table (<10 nm accuracy)A second independent tip is used for deposition, manipulatLRQ��HOHFWULFDO�SURELQJ�«

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Determination of minimal force required for deposition

Point list with increasing Excessive forcez displacement of the table

No shear.Best conditions

Arbitrary pattern defined by mouse clicking

IntroductionIntroduction DipDip--PenPen IonscopeIonscope Bioforce/BioplumeBioforce/Bioplume NADISNADIS OutlookOutlook

Interfaced NADIS patterningInterfaced NADIS patterningInterfaced NADIS patterning

35 m

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Nano-positioning processNanoNano--positioning processpositioning process

1. NADIS deposition

2. Translation under AFM imaging tip

3. AFM imaging

4. Positioning NADIS tip on the target

5. Result

IntroductionIntroduction DipDip--PenPen IonscopeIonscope Bioforce/BioplumeBioforce/Bioplume NADISNADIS OutlookOutlook

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Test printing between grooved target

Test printing on top of metallic electrodes

Accuracy:x ~ y ~ 100 nm

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Preliminary resultsPreliminary resultsPreliminary results

570nm

Reference spots

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20 nm colloidal PS on SiO2

IntroductionIntroduction DipDip--PenPen IonscopeIonscope Bioforce/BioplumeBioforce/Bioplume NADISNADIS OutlookOutlook

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Opening of PS-P2VP micelles

Applications to generic surface patterningApplications to generic surface patterningApplications to generic surface patterning

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IntroductionIntroduction DipDip--PenPen IonscopeIonscope Bioforce/BioplumeBioforce/Bioplume NADISNADIS OutlookOutlook

Main current limitationMain current limitationMain current limitation

Evaporation of the liquid from the reservoir

Two options: - Controlled atmosphere

- On-chip microfluidic canal

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Dip-Pen Nanolithography

Ionscope lithography

Bioforce/Bioplume systems

NADIS deposition system

Parallel SPM nanopatterning

Outlook

IntroductionIntroduction DipDip--PenPen IonscopeIonscope Bioforce/BioplumeBioforce/Bioplume NADISNADIS OutlookOutlook

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Combining sub-100 nm lateral resolution and cm-scale patterning

All SPM-based lithography techniques are intrinsically slow.Parallelizing the writing process is a necessary step for generalizing their use.

For Dip-Pen Nanolithography:

Year Parallel tips1999 12000 82002 322005 250

Science 2000, 288, 1808Small 2005, 1, 940

IntroductionIntroduction DipDip--PenPen IonscopeIonscope Bioforce/BioplumeBioforce/Bioplume NADISNADIS OutlookOutlook

2XWORRN�± SDUDOOHO�ZULWLQJOutlook Outlook ±± parallel writingparallel writing

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Combining sub-100 nm lateral resolution and cm-scale patterning

- 55 000 Tips in 2D array- Feature resolution : ca. 60 nm- Map writing : 8773 dots of 80 nm in a 14.5x14.5 m2 bitmap

55 000 copies = 4.7x108 features in 30 mins !- Centimeter-scale regular patterning ( >99% pens are working)

2XWORRN�± PDVVLYHO\�SDUDOOHO�ZULWLQJOutlook Outlook ±± massively parallel writingmassively parallel writing

C.A. Mirkin et al., Angew. Chem. Int. Ed. 2006, 45; Nature Nanotech. 2007, 2, 145.

IntroductionIntroduction DipDip--PenPen IonscopeIonscope Bioforce/BioplumeBioforce/Bioplume NADISNADIS OutlookOutlook

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H. D. Espinosa et al., Proc. MEMS & Nanotech. 2003, p.235

2XWORRN�± PLFURIOXLGLFV DQG�SDUDOOHO�ZULWLQJOutlook Outlook ±± microfluidicsmicrofluidics and parallel writingand parallel writing

Generalizing to any solution or suspension

In process for NADIS and BioPlume.Partially solved for Dip Pen

IntroductionIntroduction DipDip--PenPen IonscopeIonscope Bioforce/BioplumeBioforce/Bioplume NADISNADIS OutlookOutlook

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10 nm

1 zL

100 nm

1 aL

1 m

1 fL

10 m

1 pL

100 m

1 nL

1 mm

1 L

OutlookOutlookOutlook

IntroductionIntroduction DipDip--PenPen IonscopeIonscope Bioforce/BioplumeBioforce/Bioplume NADISNADIS OutlookOutlook

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AcknowledgementsAcknowledgementsAcknowledgements

BioplumeLiviu NicuChristian BergaudThierry Leichle

NADISHarry Heinzelman$QGUp 0HLVWHU

7KLHUU\�2QGDUoXKXAiping Fang

BioplumeBioplumeLiviuLiviu NicuNicuChristian Christian BergaudBergaudThierry Thierry LeichleLeichle

NADISNADISHarry Harry HeinzelmanHeinzelmanAndrAndrpp MeisterMeister

Thierry Thierry OndarOndaroouhuuhuAipingAiping FangFang