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Lecture2021 SurfaceModificationandPatterning

Unlessotherwisenoted,sourceInformationforthefollowingslides: 1) B.Ratner,A.Hoffman,F.Schoen,andJ.Lemons:BiomaterialsScience, 2nd edition(SanDiego:ElsevierAcademicPress.2004). 2) Modifiedfrom:Anne Mayes3.051J/20.340JMaterialsforBiomedical Application,MIT,http://ocw.mit.edu,

SelfAssembledMonolayers

TerminalFunctionalGroup Spacer/LinkerGroup Ligand/HeadGroup ModelSubstrate

SelfAssembledMonolayers

Advantages
Longchainaliphaticmoleculesare fullyextendedtomaximizepacking densityandvander Waalsinteractions Formationfacilitatedonplanarand/or curvedsurfaces Introducealmostanyfunctionalgroup onthesurface

MostwidelystudiedSAMs:
goldalkylthiolate alkylsilane

SH SiH3

Disadvantages

DepositionMethods:
vapordeposition electrodeposition electroless deposition

Defectsareinevitable Mechanicallyandchemicallyfragile Functionalgroupsonlyatthesurface (2D)

Selfassembledmonolayers onsurfaces(SAMs)

SelfassembledmonolayersonAusurfaces:MODEL
ThemostpopulartypeofSAMisthatformedbythechemisorption oflongchainalkanethiol moleculesoncleangoldsurfaces.Themaindrivingforcesforthisselfassemblyprocessare i) TheformationofSAubonds(bondingenergyestimatedtobe4050kcal/mol),and ii) ThefavorablelateralVander Waalsinteractionsamongthealiphaticchainsofneighboring alkanethiol molecules Parameters:Concentration(high),Solvents,Temperature,ReactionTime,PurityofSolutions, CleanlinessofSubstrates
Determinessurfaceproperties Presentschemicalfunctionalitygroups OrganicInterphase (13nm) Provideswelldefinedthickness Actsasaphysicalbarrier Alterselectronicconductivityandlocal opticalproperties MetalSurfaceInterface Stabilizessurfaceatoms Modifieselectronicstates

Selfassembledmonolayers onAusurfaces

Wheredoes

H go?

TheseSAMsarepreparedsimplybyexposingacleangoldsurfacetoasolution ofthealkanethiol.Nospecialequipmentorconditionsarerequired.Foralkanethiols Withchainslongerthan10carbonatoms,itisgenerallytruethat: 1) Astable,organizedanddenselypackedmonolayerisreadilyformedontheAusurface. 2) Thethicknessofthemonolayerisdirectlyproportionaltothelengthofthealkane thiol chain.Typicalthicknessesrangefrom1to3nm. 3) Themainaxesofindividualmoleculesaretiltled byanangleofca.30degfromthenormal tothesurface.

Selfassembledmonolayers onAusurfaces
SurfaceImpurities Defectsatgold Stepedges Vacancyislands Defectsat Goldgrain boundaries Exposed Chainat Goldstep edges

DefectsatSAM Crystaledges

Schematicillustrationofsomeoftheintrinsicandextrinsic DefectsfoundinREALSAMsformedonpolycrystallinesubstrates

Selfassembledmonolayers onAusurfaces
SAMsareapowerfulmeanstoaccomplishchemicalmodificationofasurface,andare Wellsuitedforstudiesinnanoscience andtechnologybecause 1) Theyareeasytoprepare. 2) Theyfromonobjectsofallsizesandarecriticalcomponentsforstabilizingandadding functiontopreformed,nanometerscaleobjects(forexample:thinfilms,nanowires, colloids,andothernanostructures). 3) Theycancoupletheexternalenvironmenttotheelectronic(currentvoltageresponses, electrochemistry)andoptical(localrefractiveindex,surfaceplasmon frequency) propertiesofmetallicsurfaces. 4) Theylinkmolecularlevelstructurestomacroscopicinterfacialphenomena,suchas wetting,adhesion,andfriction.
Thefigurebelowillustratesanotherimportantfeature OfSAMs.Syntheticmodificationofthethiol permitsthe Attachmentoffunctionalgroups(R)tothemonolayer.

BiomaterialApplicationsofSAMs

ExamplesofSAMsforsensorapplications

BiomaterialApplicationsofSAMs

ProteinimmobilizationofHistaglabeledproteins

ControlledCellAdhesion

UltrathinSurfaceCoatings
Ultrathinpolymerfilms filmsorcoatingslessthan100nminthickness Developsyntheticmethodologiesandcharacterizationcapabilitiesfor ultrathinfilms
<100nmthickness

Bulkpropertiesandthesurfacedeterminestheperformanceofamaterial Controloftheinteractionbetweenthematerialanditsenvironment Coatingsserveasabarrierwiththehostileenvironmentandallowsforprotectionagainst corrosionorotherchemicalorphotochemicaldegradation

GraftingTovs.GraftingFrom
Mushroom:non interacting regime Crossover regime: mushroomto brushtransition Brush:highly stretchedregime

h ~ N 1 / 3
hN A MN
2 Rg

h ~ N 0

D
graftingto Surfaceboundmonomer graftingfromorSIP

3.73.8

614?

=reducedtetheringdensity

=graftingdensity h=thickness N=degreeofpolymerization NA =Avogadrosnumber MN =molecularweightof polymer

Chen,W. et.al.PhysicalReviewLetters. 2004,93,#2.Milner,S. et.al.Science. 1991,251,905.

GraftingTovs.GraftingFrom

Graftingto

Graftingthrough

Graftingfrom

Graftingto
Physisorption:Adsorptioninwhichtheforcesinvolvedareintermolecularforces (vanderWaalsforces) Chemisorption:Adsorptioninwhichtheforcesinvolvedarevalenceforces(i.e. chemicalbondformation) Bothcasesrequiresuitableendfunctionalizedpolymerswithanaffinitytowardsa substratesurface Facile,butwithmanylimitations!!(i.e.lowgraftingdensity)

Advincula,R.(Ed.)PolymerBrushes2004WileyVCH:Weinheim.

GraftingFrom

Graftingto

Graftingthrough

Graftingfrom

Graftingfrom
Aninitiatormoleculeisdepositedonasurfacebymeansofaselfassembly processviathereactionofananchorgrouptosuitablesurfacesites,and subsequently,chainsaregrownonthesurfacefromtheinitiatingsite. Controlledfilmthickness,homogeneoussurfacecoverage,highlyfunctionalized surfaces Highbrushdensity:avg.distancebetweengraftingpoints<radiusofgyration(Rg). Accesstocomplexarchitecturesonthesurface(i.e.blockcopolymers)using controlledradicalpolymerizationtechniques

Advincula,R.(Ed.)PolymerBrushes2004WileyVCH:Weinheim.

GraftingtoChemistries

SurfaceInitiatedPolymerization
PolymerBrushes

MonomerA

MonomerB MonomerA

MonomerB MonomerA

(1)

(2)

Homopolymer Brush
Adhesion Corrosionresistance Wettability Biocompatibility

BlockCopolymer Brush
Nanostructured surfaces Environmentally responsivethinfilms

StatisticalCopolymer Brush
Tailoredfunctionalityw/o segmentationand segregation Stableexpressionof complexchemistriesat interface

CommonMonomers

BrushArchitectures

PhotoinitiatedSIP
Synthesisofsurfacereactivephotoinitiator Irgacure2959 modifiedinitiator designedwithether linkage improved stability

Microchannelreactor Requiresonly400L monomersolution


Hensarling,R.;Doughty,V.;Chan,J.;Patton,D.J.Am.Chem.Soc.2009,131,1467314675. Murataetal.Macromolecules 2007,40,54975503. Schuh etal.Adv.Mater.200921, 4706 4710.

ControlledRadicalSIP
Examplesofnitroxidemediatedpolymerization

Senaratne,W.;Andruzzi,L.;Ober,C.Biomacromolecules 2005,6,2427.

ControlledRadicalSIP
ExampleofSIATRP

ControlledRadicalSIP:RAFT

Postmodification ofPolymerBrushes

R.Barbey etal.Chem.Rev.,2009,109 (11),54375527

Ex.1:ClickingPolymerBrushes
ynemoietiesserveasreactive handlesforpostpolymerization modification Largelibraryofcommercially availablethiols,common functionalgroupinbiomolecules Highthroughput,rapidreaction kinetics quantitativeconversion inminutes

Advantage greatly reducessyntheticeffort toproducemultiple functionalmonomers


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Hensarling,R.;Doughty,V.;Chan,J.;Patton,D.J.Am.Chem.Soc.2009,131,1467314675.

MolecularLayerDeposition(MLD)
MLDisanemergingdepositiontechniqueforultrathinorganicfilms Reactantsundergoselflimiting,sequentialreactionsresultinginfilm growthalayerbylayermanner MLDuseshomobifunctionalorganicmonomerstobuildoligomericthin films,i.e.acidchloridesandamines Advantages Precisecontroloverfilmthickness Conformalcoatingofsurfaces Unprecedentedcontroloverthefilmcomposition Developedforthegrowthofpolyamides andpolyimidesandrecentlyextendedto organicinorganichybrids
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StevenM.George;Chem.Rev. 2010,110,111131.

Ex.1:MolecularLayerDeposition(MLD)
ABBinaryReactionSequence
MLDofpoly(pphenylene terephthalamide) (PPTA)

SchematicrepresentationofMLDusingselflimitingsurface chemistryandanABbinaryreactionsequence.(Reprintedfrom Chem.Rev.2010,110,111131.Copyright2007American ChemicalSociety.)


StevenM.George;Chem.Rev. 2010,110,111131.

IllustrationofsurfacechemistryforPPTAMLD usingterephthaloyl chloride(TC)andp phenylenediamine (PD)asreactants(George, S.;Yoon,B.;Dameron,A.Acc.Chem. 28 Res. 2009,42,498508.)

Ex.2:MolecularLayerDeposition(MLD)
HybridMLDFilms
Accomplishedusinginorganicand organicreactants Aluminum,silicon,titanium exampleshavebeenreported

FilmthicknessfromXRRmeasurementversusnumber ofMLDcyclesforABCalucone growthat150C.

Illustrationofthesurfacechemistryforthethree stepABCcyclewithTMA,EA,andMAasreactants; ReprintedfromGeorge,S.etal.Acc.Chem. Res. 2009,42,498508 29

Ex.3:MolecularLayerDeposition(MLD)
HybridMLDFilms
Siliconexample 1)Acyclicazasilane (AZ),suchas2,2 dimethoxy1,6diaza2 silacyclooctane,canreactwitha surfacehydroxyltocreatea siliconoxygenbond 2)Thecyclicazasilane alsounfolds, leavingaminespeciesattheterminal surface 3)Acycliccarbonate,suchasethylene carbonate(EC),canthenreactwitha surfaceaminetoformaurethane linkage
Illustrationofsurfacechemistryinvolvingtworingopening reactionswithAZandECasreactants.Reprintedfrom 30 George,S.etal.Acc.Chem.Res. 2009,42,498508

MLDLimitations
Challengesofperformingorganicchemistryinthegasphase
Findingandutilizingorganicreactantsthathavesufficientvapor pressure Understandingtheeffectofthesolutionphaseonthereaction.Many organicreactionsarecatalyzedbyacidorbaseorinfluencedby solvationeffectsthatareabsentinthegasphase Porousnatureofpolymersleadstodiffusionofgasphasereactants intothefilmleadingtobothsurfaceandbulkgrowthmechanisms

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LayerbyLayer(LBL)Assembly

LBLassemblyisawellestablishedmethodforproductionofmultilayered thinfilms Assemblybasedonavarietyofforceshavebeendemonstrated;i.e. electrostatic,hydrogenbonding,covalent,etc. Solutionpropertiesdictateassembly:concentration,pH,ionicstrength, temperature

Decher,G.Science 1997,277,12321237.

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LayerbyLayer(LBL)Assembly
Applicabletoabroadrangeofsubstratesurfaces Applicabletoabroadrangeoforganicmolecules,polymers, nanoparticles,nanotubes,biomolecules,.etc.(Highly versatileapproach!!) Conformalcoatingswithcontrolovercompositionand stratification
polyelectrolyte polyelectrolyte

+ ` + + + + +
+ + + + + + +

+ + + + +

+ +`+ + + +
+ + + + + + + + + + + +

Colloid particles

+ + + + + +

Hollow sphere shells

Polyelectrolytes coated-particles

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Example1:CovalentClickLBL
Hydrogenbondedassemblywiththiolene clickstabilizationofthemultilayers UVinducedthiolene reactionfacilitatesrapid crosslinkingbetweenlayers Excessthiolpresentattheparticleinterface facilitatesformationoflowfoulingLBLcoated capsules

Fluorescenceintensityof3mdiameterSiO2 particlescoatedwith(PVP/PMATHIOL/PVP/PMAENE) multilayersasafunctionoflayernumber

Connal,L.etal.Chem.Mater. 2009,21,576578.

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Example2:CovalentClickLBL

Microscopyimagesof3mdiametersilicaparticlescoatedwith(PVP/PMATHIOL/PVP/PMAENE)2/PVPand resul ngPMATEcapsules.(a)PhasecontrastimageofUVirradiatedcoatedparticlesatpH4andthe correspondingfluorescencemicroscopyimage(inset).(b)FluorescencemicroscopyimageofUVirradiated PMATEcapsulesatpH7.(c)Transmissionelectronand(d)scanningelectronmicroscopyimagesofPMATE capsulesatpH7.PMAwaslabeled withAF488.


Connal,L.etal.Chem.Mater. 2009,21,576578.

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Example2:CovalentClickLBL

FluorescenceintensityofPVP/PMAcoatedparticles(of3mdiameter)afterincubationwithfluorescently labeled proteins,asmeasuredbyFC.Blankbackgroundfluorescenceofthesilicaparticlesbeforeincubation; Sibaresilicaparticles;andPMAUVtreated(PVP/PMATHIOL/PVP/PMAENE)2coatedparticles.PEG1and PEG2:UVtreatedparticlescoatedwith(PVP/PMATHIOL/PVP/PMAENE)2exposedtothemonofunctional PEGacrylateandmaleimidePEGsuccinimidyl ester,respectively.


Connal,L.etal.Chem.Mater. 2009,21,576578.

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LBLApplications
Energy
Photovoltaics Batteries FuelCellMembranes

Electronics
Organiclightemittingdiodes(OLEDs)

Biomaterials
Drugdelivery Antifoulingcoatings

Membranes
Gasbarrier/separationmembranes

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AdsorptionfromSolution

AdsorptionfromSolution

SurfaceSegregation

Figure6SurfacesegregationofcombpolymerinPLAblends measuredbyXPS.()Expectedsurfacecompositionforno segregation.()Surfacevolumefractioncombpolymer calculatedfromXPSdataforunannealed PLA/C1blends.() Surfacevolumefractioncombpolymerforblendsannealed 4daysat70CinH2O.()Surfacevolumefractioncomb polymerforblendsannealed4daysinavacuumat120C.


Biomacromolecules,2001,2(2),pp 545556

PlasmaTreatment

PlasmaTreatment

PlasmaModification

PlasmaSprayedCoatings

VacuumPlasmaSpray
Vacuumplasmaspraying(VPS)isa technologyforetchingandsurface modificationtocreateporouslayers withhighreproducibilityandfor cleaningandsurfaceengineeringof plastics,rubbersandnaturalfibers Thisprocesscanimproveproperties suchasfrictionalbehavior,heat resistance,surfaceelectrical conductivity,lubricity,cohesive strengthoffilms,ordielectric constant,oritcanmakematerials hydrophilicorhydrophobic. Theprocesstypicallyoperatesat 39120Ctoavoidthermal damage.

Plasmasprayingistheonlycommercially acceptedmethodforproducing hydroxyapatitecoatings

OtherOrthopedicBiomaterialsTreatments

Fig. 1. electrolytic ZrO2 coating on CoCrMo implant alloys of hip prosthesis: SEM observations of deposited specimen (a) after natural drying, then annealed for 120 min at (b) 773 K and (c) 873 K.

PatternedSurfaceModification
Patternsdesiredfor: Gene,protein,andcellmicroarrays Biosensors Combinatorialstudies Directedcellmigration,cellsorting Structuringengineeredtissues

Microcontact Printing

Whitesides etal.Biomaterials 20,1999, 23632376.

InkjetPrinting
w

Photopatterning Methods
Ex.SelectivecleavageunderUVlight

Nitrobenzyl methacrylateunitsofcopolymercleavedunderUVtocreate negativelychargedregions.Usingphotolithographymaskallowscreation ofpatternedanionregions(shownstainedwithacationicdye)

J.Am.Chem.Soc.,2004,126 (30),pp91709171

Photopatterning Methods

J.Am.Chem.Soc., 2004,126 (30),pp 91709171

Figure2Schematicprocedureofdualstreptavidinpatterning.

Figure3Fluorescentmicroscopyofdualstreptavidinpatternedsurface.(a)SAv TRfluorescence.(b)SAvFITCfluorescence.(c)Overlay.

Photopatterning Methods
Ex.SelectivecrosslinkingunderUVlight

Figure4AFMimagesoftheUVpatterned (PAH3.0/PAArVBA 3.0)20 sampletakenin aqueoussolutionat(a)pH7and(b)8.

Figure6Demonstrationof3Dpatterning. PhotographoftheUVpatterned[(PAH 8.5/PAArVBA 3.5)10/(PAH8.5/PAA3.5)5]4.5 filmafterinducednanopore formation. Thediameterofthesmallcircleis4mm.


Langmuir,2006,22 (13),pp 59585962

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