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12:Nanoparticlesynthesis by yp precipitation p methods

March2,2009

Nanomanufacturing UniversityofMichigan
ME599002/Winter2009

JohnHart
ajohnh@umich.edu http://www.umich.edu/~ajohnh
2009 A.J.Hart 1

Announcements
ProjectproposalsdueW Mar/4;topicsconfirmedMar/11 HW3(outbeforeW)dueFMar/13 Nolecture MMar/16 / EXAM WMar/18 HW1recap Mean103/127 Std12 Max123 Min73

2009 A.J.Hart 2

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Recap:surfaceplasmonresonance(SPR)

Kellyetal.,J.Phys.Chem.B107:668,2003. Barnesetal.,Nature424:824830,2003.

2009 A.J.Hart 3

Biomolecularsensing

Biacore:commercialSPRinstruments http://www.biacore.com/lifesciences/technology/introduction/data_interaction/index.html http://www.biosensingusa.com/Application101.html Choietal.,CollidsandSurfaces,A313314:6556592008.

2009 A.J.Hart 4

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Biomolecularsensing

Healyetal.,TrendsinBiotechnology25(3):125131,2007

2009 A.J.Hart 5

SinglemoleculeRamanspectroscopy (SERS) hotspots!

VanDuyne,etal.;Aroca,etal.

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Plasmoninducedcrystalgrowth@hotspots

Jinetal.,Science294:19011903,2001.

2009 A.J.Hart 7

Emergenceofabimodalsizedistribution

Jinetal.,Nature425:487490,2003.

2009 A.J.Hart 8

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Plasmoniclithography

Srituravanichetal.,NatureNanotechnology3:733737,2008.

2009 A.J.Hart 9

Srituravanichetal.,NatureNanotechnology3:733737,2008.

2009 A.J.Hart 10

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Plasmoninducednanoparticleheating

Govorov,NanoToday 2(1):30,2007

2009 A.J.Hart 11

Plasmoninducednanoparticleheating

Govorov,NanoToday 2(1):30,2007

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MeasuringtemperaturerisecausedbySPR heating

Govorov,NanoToday 2(1):30,2007

2009 A.J.Hart 13

Govorov,NanoToday 2(1):30,2007

2009 A.J.Hart 14

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Todaysagenda
Thermodynamicmodelofclustergrowthinsolution (gas/liquid,liquid/solid) Diffusionlimitedandreactionlimitedgrowthregimes Theoryofsizebroadeningandfocusing Examples

2009 A.J.Hart 15

Todaysreadings(ctools)
Sugimoto,Preparationofmonodispersedcolloidal particles
Throughpage73,neededasbackuptolecturenotesonly

Pengetal.,KineticsofIIVIandIIIVcolloidal semiconductor i d nanocrystal lgrowth: h focusing f i of fsize i distributions Burdaetal.,excerptfromChemistryandpropertiesof nanocrystalsofdifferentshapes

Spansmethodsofmakingnanoparticles,nanowires/tubes,and selfassembly

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Size andstructuredependentproperties

Nanoclusters
Magic#sofatoms nmsize

/Nanoparticles
100s1000sofatoms nm100nmsize

Nanowires/Nanotubes

Sheets
2009 A.J.Hart 17

Filled Hollow 1atomthick nm100nmdia,uptommlengthandbeyond!

<100>CdSe

<001>CdSe

1.5nm
Frankel,Bawendi.

2009 A.J.Hart 18

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Anisotropy

GlotzerandSolomon.NatureMaterials6:557562, 2007.

2009 A.J.Hart 19

Start:nucleate!

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Nucleateand grow

2009 A.J.Hart 21

Nucleatethen grow

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Thebestwaytomakemonodispersenanostructuresis toemployalargenumberofverysmallpeople.

2009 A.J.Hart 23

Strategy:separatenucleationandgrowth byprocesscontrol

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Condensationfrom vaporathighinert gaspressure Addoxygento oxidizeparticles, stoppinggrowth gro th

2009 A.J.Hart 25

Typesofnucleation
Homogeneousnucleation:solutemoleculeswithinaliquid combinetoproducenuclei;nosolidinterfacepresent Heterogeneousnucleation: Anucleusformsonapreexisting surfaceofanothermaterial(e.g.,impurity,vesselwall) Secondarynucleation:Occursatapreexistingseedofthe samematerial,orbyaggregationofparticles

2009 A.J.Hart 26

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Criticalclustersizesforsomemetals

2009 A.J.Hart 27

Evolutionofprecursorconcentrationduring nucleationandgrowth(LaMer,1950)

Concentrationchangeswithtimeasmonomerisdepleted
Sugimoto,Adv.ColloidInterfaceScience 28:65,1987.

2009 A.J.Hart 28

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Modelingdiffusiontotheparticle

Cb =bulkconcentrationofprecursor(monomer)insolution Ci =precursorconcentrationattheinterface Ce =solubilityoftheparticle(concentrationthatwouldbein equilibriumwithsolutionifparticlewereatcriticalsize)

Sugimoto,Adv.ColloidInterfaceScience 28:65,1987. 2009 A.J.Hart 29

Theory:sizebroadeningandfocusing

ROCofaverageradius

ROCofstandarddeviation ofradius

Sugimoto,Adv.ColloidInterfaceScience 28:65,1987.

2009 A.J.Hart 30

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Results:sizebroadeningandfocusing

Pengetal.,JournaloftheAmericanChemicalSociety 120:5343,1998.

2009 A.J.Hart 31

MonodispereCdSebysizefocusing

Pengetal.,JournaloftheAmericanChemicalSociety 120:5343,1998.

2009 A.J.Hart 32

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Monitoringparticlesizebyoptical absorptionandemission

Pengetal.,JournaloftheAmericanChemicalSociety 120:5343,1998.

2009 A.J.Hart 33

Anothermethod:low hightemperature
70oC

240oCnucleation 320oCgrowth

Parketal.,NatureMaterials 3:891,2004.

2009 A.J.Hart 34

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Controllingsize:changesolvent(boilingpt) andacidconcentration

Parketal.,NatureMaterials 3:891,2004.

2009 A.J.Hart 35

Differentmaterials:changemetalsalt precursor
Fe CoO MnO

Parketal.,NatureMaterials 3:891,2004.

2009 A.J.Hart 36

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Isprecisefocusingenough?No!
Recallsecondarynucleation(aggregation) Inhibitaggregationby,forexample: Addingacappinglayer(e.g.,surfactant)atacriticalsize Doublelayerrepulsion,i.e.,precipitatewhentheparticles arecharged Morewhenwediscussselfassemblyinsolution

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