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SurfaceModificationSelfAssembly

Sang-GookKim

CapillaryElectrophoresis(CE)

+

E

-

--

-

-

-

---

- -

-

-+

+

+

+

+

+ +

+

+ +

+

+ +

-

Felec

-- -

-

---

-

Fcounterion

Fdrag

φ0

++++

----

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SurfaceTensionFlow

• LaplacepressurefromYoungEqn. r

2γPLaplace ~ r

r3r2

Electrophoreticmobility• Mobility (μ):Particlevelocityunderunitelectricfield

V!ep E

!= µ

V

Fdrag = 6πηrV

r

Fluidwithviscosityη

Felectric = qE

q

+E

! qE!

Vep = 6πηrq

µEF = 6πηr!

"#

$

%&

(Hückel equation)

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Dielectrophoresis• Apolarizable particleis

attractedtoaregionofhighelectricfieldstrength

Voldman, Annu.Rev.Biomed.Eng.(2006)

HighSpedSorting

https://www.youtube.com/watch?v=4zsSET80jpQAgresti,PNAS2010

This image has been removed due to copyright restrictions.Please see part (a) of the image at http://nano.tu-dresden.de/pubs/reprints/covers/ 2012_Master_Gur.png?id=3679.

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Dielectrophoresis• Apolarizable particleis

attractedtoaregionofhighelectricfieldstrength

• Directionofforceisindependentofdirectionofelectricfield

• Usefulformanipulatingcellsandmicroscaleparticles

Voldman, Annu.Rev.Biomed.Eng.(2006)

Polarization

• Atomicpolarization• Ionic,molecular…• Interfacialpolarization

http://www.nanotech.upenn.edu/nuggets/0032.html

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copyright restrictions. Please see http://www.nanotech.upenn.edu/nuggets/0032.html

This image has been removeddue to copyright restrictions.Please see http://www.nanote

. ch.upenn.edu/nuggets/0032.html.

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DielectrophoresisIfasuspendedparticlehaspolarizability higherthanthemedium, theDEPforcewillpushtheparticletowardregionsofhigherelectric field(positiveDEP).Ifthemediumhasahigherpolarizability thanthesuspendedparticle,theparticle isdriventowardregionsoflowfieldstrength(negativeDEP).

DEPForce

• r – radius• E – nonuniform electric field• -permittivity of medium• * - Complex permittivity• Re[K] – Clasius-Mossotti Factor where

23 ]Re[2 EKrF m ∇= επ

mε

ε * *

K p −εm=ε * 2 *p + εm

This image has been removed due to copyright restrictions.Please see the image on Page 16 of http://nanoparticles.org/pdf/noh.pdf.

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• At low frequencies:

• At high frequencies:

• Polarization Factor (K) can be switched between positive or negativevalues

mp

mpKσσ

σσ

2+−

≈

mp

mpKεε

εε

2+−

≈

Clausius-Mossotti Factor

SingleCellCage

Voldman, MIT

This image has been removed due to copyright restrictions.Please see the image on Page 29 of http://nanoparticles.org/pdf/noh.pdf.

••

λ

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This image has been removed due to copyright restrictions.Please see Figure 1 at https://www.mems-exchange.org/MEMS/processes/lithography.html.

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PDMSembossingprocess

• Masterfabrication(MEMS)• MoldbyPDMScasting

• Bondontoasubstrate

• Multi-layeredPDMS

15

Micro-Injection

16

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LaserAblation

17

Dip-pennanolithography(DPN)Mirkin,Northwestern

OliverGescheke,DTU,2004

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Whitesides andLove,ScientificAmerican,Sept.2007

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Microcontactprinting(μCP)• Conformalstampis“inked”

• Stampisplacedincontactwithsurface(non-planar)

• Moleculestransfertosurfacewherestampmakescontact

Micheletal.,IBMJ.Res.&Dev.,45,697(2001)

TransportofmoleculesinμCPPathsoftransportofmoleculesinμCPDiffusionwithinPDMSDiffusiononsurfacesEvaporation-condensationLiquidflow/spreading

EffectofthiolconcentrationexaminedbySEM(ECT- eicosanethiol,20carbons)Increasingconcentrationdecreasesdefects,butincreasespatternwidth

Micheletal.,IBMJ.Res.&Dev.,45,697(2001)

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This image has been removeddue to copyright restrictions.Please see Figure 1 in http://www.aspe.net/publications/Short%20Abstracts%2013A /3751.pdf.

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Alkanethiolatedself-assembledmonolayer(SAM)

Loveetal,Chem.Rev.105,1103(2005) Mrksich etal,Expt.CellRes.235,305(1997)

Silanization ofglassAminoSilane

Possibleendgroups:NH2,SH,OEG/PEG,epoxy,CF3,CH=CH2,COOH,CHO,…

•Morevariety thanalkanethiols•Lessrobust•Lesseasilyordered

Jal etal.,Talanta 62,1005(2004),Macanovic etal,NucleicAcidsRes.32(2004)

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Modificationofsurfaces

• Alkane-thiols orsilanes enablefunctionalizationofgoldandglasswithdifferentendgroups

• Avarietyofreagentsareavailabletojoin theseendgroupswith– Groupspresentonother surfaces– Groups(NH2,COOH,SH)presentonbiomolecules– Othermolecules(dyes,biotin,etc.)

MechanicalconsiderationsinμCP• Conformal contactrequires stamp

flexibility• Largeaspectratiostampscan

collapseordistort• Largegapscancollapse.• Smudgingduring placingandlifting

offstamp

XiaandWhitesides,Ang.Chem.Int.Ed.,37,550(1998)Micheletal.,IBMJ.Res.&Dev.,45,697(2001)

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DrugScreening• “Key”and“Lock”• Chemicalcompounds tobiologicaltargets• HighThroughputs Screening,100K/day

25 faculty.washington.edu/stenkamp http://en.wikipedia.org/wiki/Antibody pbs.org, Leeetal.,LabChip9,2267(2009).

DNAstrandhybridization

CompoundLibrary

Biomolecularrecognition• Biomoleculescan

“recognize”othermoleculesandspecificallybindtothem

– Enzymesandtheir substrates– Antibodies andantigens– Avidins andbiotin

Antibody-antigeninteraction

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This image is in the public domain.

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Patterningofantibodies usingstreptavidin-biotin interactions

Nanowire sensors:Surfacemodification

Patolsky etal,Nat.Protocols,4,1711(2006)

This image has been removed due to copyright restrictions.Please see http://www.nature.com/nprot/journal/v1/n4/

images/nprot.2006.227-F11.jpg.

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Self-Assemblyas·sem·blyn. pl. as·sem·blies

a.. b.The putting together of manufactured parts to make a completedproduct, such as a machine or electronic circuit. Source: The American Heritage® Dictionary of the English Language, Fourth Edition

~$2 trillion

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DNAmicroarrays

en.wikipedia.org/wiki/DNA_microarray

This image is in the public domain.

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This image is in the public domain.

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Complexityofmicrochipassembly• Oldassemblytechnologyformicrostructures

• Tyrannyofnumbers

31

MonolithicDesign

S.G.Kim,CIRP2006,STCA

J. KirbyofTI(1958)R. Noyce,Intel(1959)

- Design forassemblyatsmallscales?

- Designtoolsforsmallscaleproducts?

- HowtoachievecommercialsuccessofMEMSproducts?

AssemblyofMolecularMachines? 32

Image courtesy NASA Advanced Supercomputing Division

On Dec. 9, 2003 The New York Times carried a story on the debate: "Yes, They Can! No, They Can't: Charges Fly in Nanobot Debate". A week later, the Times published the following(edited) letter from Dr. Drexler.

E. Drexler, Proc. Natl. Acad. Sci. USAVol. 78, No. 9, pp. 5275-5278, September 1981

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33

Gulliver’s travel to Lilliput

Gulliver, 6ft tall, 160 lb weightLilliputian, 6 in tall, 1.5 ounce.

Size of lego?

9.6 mm by 8 mm800 µm by 660 µm

Self-assembly?Gulliver in Broadingnag?Assemby by Bacteria?

CarbonNanotube 34

• Discoveredduringthestudyofarc-dischargeproducts. Nature, 354, 56 (1991)

• Rolledgraphenesheetsofcarbonatoms,coaxiallyarrangedinacylindricalshape.– SWNT, single-wallednanotube(1<d<3nm.)– MWNT,multi-wallednanotube

Dekker group, Nature, 393, 49 (1998)

Howtoassemble?

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Patternmatching

37

FluidicSelfAssembly

38

Fluidicself-assemblyofGaAsLEDsonatemplatedSisubstrate.

AlienTechnologyFluidic self assembly

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Fluidic Self-Assembly

Boringer group,Univ.Washington

This image has been removeddue to copyright restrictions.Please see http://www3.u-toyama.ac.jp/maezawa/Research/Figures/FSAImage.JPG.

��Howe group

S. Smith and Alien Co.

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Lieber Group Langmuir-Blodgett approach (raft)

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R.H.M. Chan et al, Nanotechnology 15, 672-677, 2004

G. Whiteside Group, 3D Self-assembly

CapillaryShearElectricMagnetic

© Lieber Group, G. Whiteside Group, S. Smith and Alien Co., Howe Group, and IOPPublishing. All rights reserved. This content is excluded from our Creative Commonslicense. For more information, see https://ocw.mit.edu/help/faq-fair-use.

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LBAssembly

41

SEMimageofaLBmonolayerofdodecanethiol-encapsulatedgoldparticles8.3nmindiameter.The insetshows ahigh-magnificationSEMimage.Reprintedwithpermission fromRef.24S.Huangetal. , J. Vac.Sci. Technol. B19,2045,2001, Schematicillustration of themechanismfor thein-plane

orientation ofs-SWNT:(a)compression-inducedorientation intheLangmuirfilmbybarriercompression; (b)in-plane tubeorientationforfilmspreparedbyhorizontal lifting; (c)floworientation oftubesinducedbytheverticalmotionofthesubstrate.Reprintedpermission fromRef.25Y.Kim, N.Minami,W.Zhu,S.Kazaoui, R.Azumi andM.Matsumoto, Jpn.J. Appl. Phys.42,7629,2003,

DirectedNano Assembly

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CNT growth AssemblyEncapsulation

Si substrate

Ni Catalysts

CNT growth

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Pellet release

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Vertical assembly

Horizontal assembly

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Shear an SU8 blockApproach a cantilever Cure adhesive

Release the SU8 block

CNT tipped AFM probe

A single strand CNT A CNT-tipped AFM probe

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Light

ThinfimMicromirror ArrayforProjectionDisplay

CIRPGA2000

TunablePhotonics

a d

Nanoassembly ofCNTs

IEEEMEMS2005

PZTactuators

AppliedPhysicsLetters,Vol. 85,2004

AppliedOptics,Vol. 42,2003

IEEEMEMS2003

AppliedPhysicsLetters,Vol. 94,2009

EnergyHarvester,APL2011

Idealsolarenergyharvester

PMUT

Adv.Materials,2014IEEETUFFC,2015

Gooddesignisimportantatsmallscales.–KimLab

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AFMScanningResults:F-actin

10 µm10 µm 3 µm3 µm

600nm 600nm

Fluorescent Imaging 3D (height mode)

Height mode Deflection mode

Filament actin (64µl/2..3µM)In 50ml buffer solution

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Summary• Surfacesbecomemoreimportantatsmallerlengthscales

• Surfaceswithspecificfunctionalitiesaredesirableinmanymicro/nano applications

• Integrationof1)patterningtechniques,2)chemistry,and3)biomolecular interactionsprovidesuswithversatiletoolstoengineersurfaceswithspecificproperties

• Wewillexploretheseaspectsinlab#6

MIT OpenCourseWarehttps://ocw.mit.edu

2.674 / 2.675 Micro/Nano Engineering LaboratorySpring 2016

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