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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&(
dujardin@cemes.fr
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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)
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)
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
«
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
Erik DUJARDIN SPM-based surface nanopatterning 6
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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
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
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
Erik DUJARDIN SPM-based surface nanopatterning 9
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
Erik DUJARDIN SPM-based surface nanopatterning 10
IntroductionIntroduction DipDip--PenPen IonscopeIonscope Bioforce/BioplumeBioforce/Bioplume NADISNADIS OutlookOutlook
Applications (1)Applications (1)Applications (1)
Magnetic nanostructures
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);
Erik DUJARDIN SPM-based surface nanopatterning 12
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
Erik DUJARDIN SPM-based surface nanopatterning 14
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
Erik DUJARDIN SPM-based surface nanopatterning 16
Dip-Pen Nanolithography
Ionscope lithography
Bioforce/Bioplume systems
NADIS deposition system
Parallel SPM nanopatterning
Outlook
IntroductionIntroduction DipDip--PenPen IonscopeIonscope Bioforce/BioplumeBioforce/Bioplume NADISNADIS OutlookOutlook
Erik DUJARDIN SPM-based surface nanopatterning 17
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.
Erik DUJARDIN SPM-based surface nanopatterning 18
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
Erik DUJARDIN SPM-based surface nanopatterning 19
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
Erik DUJARDIN SPM-based surface nanopatterning 20
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
Erik DUJARDIN SPM-based surface nanopatterning 21
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
Erik DUJARDIN SPM-based surface nanopatterning 22
Dip-Pen Nanolithography
Ionscope lithography
Bioforce/Bioplume systems
NADIS deposition system
Parallel SPM nanopatterning
Outlook
IntroductionIntroduction DipDip--PenPen IonscopeIonscope Bioforce/BioplumeBioforce/Bioplume NADISNADIS OutlookOutlook
Erik DUJARDIN SPM-based surface nanopatterning 23
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)
Erik DUJARDIN SPM-based surface nanopatterning 28
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
Erik DUJARDIN SPM-based surface nanopatterning 29
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
Erik DUJARDIN SPM-based surface nanopatterning 30
Dip-Pen Nanolithography
Ionscope lithography
Bioforce/Bioplume systems
NADIS deposition system
Parallel SPM nanopatterning
Outlook
IntroductionIntroduction DipDip--PenPen IonscopeIonscope Bioforce/BioplumeBioforce/Bioplume NADISNADIS OutlookOutlook
Erik DUJARDIN SPM-based surface nanopatterning 31
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)
Erik DUJARDIN SPM-based surface nanopatterning 32
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).
Erik DUJARDIN SPM-based surface nanopatterning 33
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)
Erik DUJARDIN SPM-based surface nanopatterning 34
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
Erik DUJARDIN SPM-based surface nanopatterning 35
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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
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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 �
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Erik DUJARDIN SPM-based surface nanopatterning 37
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.
Erik DUJARDIN SPM-based surface nanopatterning 38
Affymetrix NanoEnabler (Bioforce) NADIS
10 m500 m
IntroductionIntroduction DipDip--PenPen IonscopeIonscope Bioforce/BioplumeBioforce/Bioplume NADISNADIS OutlookOutlook
Performance comparisonPerformance comparisonPerformance comparison
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
Erik DUJARDIN SPM-based surface nanopatterning 40
0 5 10 15 200
200
400
600
800
1000
1200
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t (s)
IntroductionIntroduction DipDip--PenPen IonscopeIonscope Bioforce/BioplumeBioforce/Bioplume NADISNADIS OutlookOutlook
A. P. Fang, E. DujaUGLQ��7��2QGDUoXKX��1DQR/HWW�����������������
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
Erik DUJARDIN SPM-based surface nanopatterning 41
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10
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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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Erik DUJARDIN SPM-based surface nanopatterning 42
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
Erik DUJARDIN SPM-based surface nanopatterning 43
IntroductionIntroduction DipDip--PenPen IonscopeIonscope Bioforce/BioplumeBioforce/Bioplume NADISNADIS OutlookOutlook
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-60
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0
20
40
0 100 200 300 400 500
z (nm)
ExpCalc
2.Rsurf = 400 nm, 2.Rtip = 300 nm
P = 1.4 104 Pa
Fexp/Fcalc = 0.53 Fexp/Fcalc = 0.53
-40
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-20
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0
10
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z (nm)
Exp
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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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
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Erik DUJARDIN SPM-based surface nanopatterning 45
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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IntroductionIntroduction DipDip--PenPen IonscopeIonscope Bioforce/BioplumeBioforce/Bioplume NADISNADIS OutlookOutlook
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Rsurf / Rtip
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Direct correlationbetween force curveand deposit size
Erik DUJARDIN SPM-based surface nanopatterning 46
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
-60
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20
40
0 100 200 300 400
z (nm)
expcalc
Erik DUJARDIN SPM-based surface nanopatterning 47
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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Erik DUJARDIN SPM-based surface nanopatterning 48
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
Erik DUJARDIN SPM-based surface nanopatterning 49
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
Erik DUJARDIN SPM-based surface nanopatterning 50
Test printing between grooved target
Test printing on top of metallic electrodes
Accuracy:x ~ y ~ 100 nm
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IntroductionIntroduction DipDip--PenPen IonscopeIonscope Bioforce/BioplumeBioforce/Bioplume NADISNADIS OutlookOutlook
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Preliminary resultsPreliminary resultsPreliminary results
570nm
Reference spots
Erik DUJARDIN SPM-based surface nanopatterning 51
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
Erik DUJARDIN SPM-based surface nanopatterning 52
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
Erik DUJARDIN SPM-based surface nanopatterning 53
Dip-Pen Nanolithography
Ionscope lithography
Bioforce/Bioplume systems
NADIS deposition system
Parallel SPM nanopatterning
Outlook
IntroductionIntroduction DipDip--PenPen IonscopeIonscope Bioforce/BioplumeBioforce/Bioplume NADISNADIS OutlookOutlook
Erik DUJARDIN SPM-based surface nanopatterning 54
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
Erik DUJARDIN SPM-based surface nanopatterning 55
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
Erik DUJARDIN SPM-based surface nanopatterning 56
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
Erik DUJARDIN SPM-based surface nanopatterning 57
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
Erik DUJARDIN SPM-based surface nanopatterning 58
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