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7/28/2019 Francesco Stella Cc i

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S u N M a G

The Su pramolecular Nano Ma terials Group

Supramolecular Materials Science

Monolayer ProtectedMetal Nanoparticles

FunctionalizedCarbon Nanotubes

Nanowires

Supramolecular Lithography Supramolecular

Nano Stamping

Jackson, Myerson, Stellacci, Nat. Mat. , 3, 330, 2004 Akthakul, Stellacci, Mayes,. Adv. Mat ., 17, 532, 2005Jackson, Silva, Hu, Stellacci, JACS. , 128, 11135, 2006

DeVries, Brunnbauer, Stellacci, Science 315, 358, 2007Centrone, Yu, Stellacci, Small , 3, 814, 2007

Barsotti, OConnell, Stellacci, Langmuir, 20, 4795, 2004Barsotti, Stellacci, J. Mat. Chem ., 16, 962, 2006

Halik, M. et al. Nature , 431, 963, 2004

Yu, Stellacci, Nano Letters , 5, 1061, 2005Yu, Stellacci, JACS , 127, 16774, 2005Yu, Stellacci, J. Mat. Chem. , 16, 2868, 2006

Wunsch, Stellacci, Prato, manuscript in prepLong, Wu, Wunsch, Marzari, Stellacci in prep..Liu, Yuan, Kong, Stellacci manuscript in prep.

NANO-MATERIALS

LITHOGRAPHY

20 m


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Metal Nanoparticles Synthesis

Metal Salt (AuHCl 4) + HS

Reducing Agent (NaBH 4)+HS

Ligand exchangereaction *

Direct mixedligands reaction **

A. C. Templeton, M. P. Wuelfing and R. W. Murray, Accounts Chem. Res. 2000 , 33, 27F. Stellacci, et al. Adv. Mat. 2002 , 14, 194

HS

HS

HS

HS


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Nanoparticle Absorption

1

2 21 2( 2 )m

=+ +

Mie theory describes the absorption, , of small metallic particles:

m

gold

m is a volume-average of the dielectric constants

( ) of the ligand molecules and the solvent

4-Aminophenyldisulfide(APS)

Electron donor

4-Fluorobenzenethiol(FBT)

Electron acceptor

5,5-Dithiobis(2-nitrobenzoic acid)(NBA)

Electron acceptor

Dimethyl (4,4 dithiobiscinnamate)(CIN)

Electron acceptor

F

SH SH

NO 2

OH

O

SH

OO

NH2

SH

Conjugated molecules:


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Absorption by Functionalized Nanoparticles

Trend in predicted by polarizability of molecules Steric hindrance of NBA molecule causes porous ligand shell,

effectively lowering relative to expected value

By Mie theory:

CIN

FBT

APS(NBA)

Increasing

522

530

510

541

0

0.05

0.1

0.15

0.2

0.25

0.3

0.35

0.4

300 400 500 600 700 800

Wavelength (nm)

A b s o r p t i o n

AminophenyldisulfideFluorobenzenethiolNitrobenzoic acidCinnamate

Spectra taken indichlorobenzene (DCB) F

SH

SH

NO 2

OH

O

SH

OO

NH2

SH

Absorption spectra for fully conjugated nanoparticles

*

*

* Chromophore absorption from ligands; unrelated to plasmon resonance


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Increasingly Conjugated Nanoparticles

518

518

522

522

528

0.1

0.2

0.3

0.4

0.5

0.6

250 350 450 550 650 750 850Wavelength (nm)

A b s o r p t i o

hexanethiol1:21:12:1conjugated

Absorption spectra for increasingly conjugated FBT series nanoparticles

Nanoparticles withvarying ratios of:

SH

F

SH

HT

FBT

(low )

and

(high )

Larger fractions of conjugated FBT make ligand shell more polarizable; demonstrates corresponding increase

Similar trends are observed in other molecule series as well

More FBTIncreasing

HT HT FBT FBT eff

ligands

V V V

+=

Spectra taken indichlorobenzene (DCB)


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Characterizing Metal Nanoparticles

2.7 nm

3 nm

TEM shows atoms in the core STM shows ligands in the shell


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Diameter =7.422nmLigand length= 1.08 nm

1.9nm

Average S-S spacing=0.409 nm

Octanethiol (C8) homoligand np

Average STM observedheadgroup spacing = 0.5

Diameter=7.418

Ligand length=1.56 nmAverage STM observedheadgroup spacing= 0.6305

Average S-S spacing=0.3646 nm

Dodecanethiol (C12) homoligand np

Based on Luedtke and Landman Faraday Discussions 2004, 125, 1-22

S =STM observed spacingx =ligand spacing at core surface (adjacent Sulfur-Sulfur distance)D =S TM observed np dimater (core +ligand shell)d =diameter of np core

Sd/2

D/2

x

S/D = x/d

Assumptions: The nanoparticle can be approximated as a sphereLigand length (L) is constant around the shell i.e. (D/2) =Constant

For a fully extended ligand chain of length L, with n carbon atoms, Use L =0.12 (n+1) nm

W. D. Luedtke and Uzi LandmanJ. Phys. Chem. B, 102 (34), 6566,,1998

Homoligand particles ligand structure


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Au (111)

STM Height Image of OT/MPA Mixed Monolayer on Au(111)

5 nm

Randomly distributeddomains of OT form in asurrounding matrix of MPA

MPA

OT

R. Smith, S. Reed, P. Lewis, J . Monnell, R. Clegg, K. Kelly, L. Bumm, J .Huthison, P . Weiss. J. Phys. Chem. B 2001 , 105, 1119-1122.

SHCOOH SH

Mixed Self Mixed Self --AssembledAssembled MonolayersMonolayers


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2 nm

a b

5 nm

c

2 nm

a b

5 nm

c

SH

MPA

OT

SHCOOH

STM Images of Rippled Nanoparticles

b

5 nm

2 nm2 nm

ab c

c d

Jackson, Myerson, Stellacci, Nat. Mat. , 3, 330, 2004Jackson, Silva, Hu, Stellacci, JACS. , 128, 11135, 2006


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Hydrophobic/Hydrophilic Ripples

a

5 nm

a

5 nm

5 nm

2 nm2 nm

ab c

c d


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Noise and Ripples

ajs6_11_12

0.4

0.5

0.6

0.7

0.8

0.9

1

4 4.5 5 5.5 6 6.5 7 7.5 8 8.5 9 9.5 10

Diameter [nm]

R i p p l e S p a c i n

g [ n m ] .007

.007'

.007''

.005

.005'

.005''

0.5 1.0 1.5 2.0 2.50.0

0.2

0.4

0.6

0.8

1.0

1.2

1.4

1.6

1.8

r i p p

l e s p a c i n g

[ n m ]

speed [um/s]

0.5 1.0 1.5 2.0 2.50.0

0.2

0.4

0.6

0.8

1.0

1.2

1.4

1.6

1.8

r i p p

l e s p a c i n g

[ n m

]

speed [um/s]0.5 1.0 1.5 2.0 2.5

0.0

0.2

0.4

0.6

0.8

1.0

1.2

1.4

1.6

1.8

n o

i s e s p a c i n g

[ n m

]

speed [um/s]

b c

5 nm5 nm1.496 m/s 5 nm5 nm1.496 m/s 5 nm5 nm1.841 m/s 5 nm5 nm1.841 m/s5 nm5 nm1.595 m/s 5 nm5 nm1.595 m/s

a005 imagetaken at0.57 m/s

Showsaverage ripplespacing of 0.699 nm0.098 nm

007 imagetaken at0.814 m/s

Showsaverageripple spacingof 0.743 nm 0.052 nm

Jackson, Silva, Hu, Stellacci, JACS. , 128, 11135, 2006


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Phase Separation on NanoparticlesPhase Separation on Nanoparticles

OT:MPA

OT:MUA

SH NH2SH NH2

Hexanethiol: p-Aminothiophenol

SH OH

O

SH

SH

Ag/-SH or /-NH 2,Fe 3O4 /-COOH,CaCO 3/COOH

SH

OT:Mercaptohexanol

SHOH


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Increasing Curvature

Flat Au (111)on Mica

OT:MPA Mixed Monolayers formed on surfaces of varying curvatures

Au on Si, with20 nm

hemispheres

Au film withAu crystals

~ 10 nm

Au film withAu crystals

~ 4 nm

10 nm 10 nm 5 nm 5 nm

Curvature EffectsCurvature Effects


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Chemistry of chain formation

SH

OH

OSH

OH

O

SHHOOC

1. Pole functionalization with 11-Mercaptoundecanoic acid (MUA)

Short reaction times allow functionalizationonly at the polar singularities

2. Two-phase reaction : interface-controlled stoichiometry

NH2NH2

1,6-Diaminohexanein water phase

Nanoparticles in toluene phase

Nano-nylon

Amide bonds

Precipitation at thetoluene-water interfaceindicates the formationof insoluble material

Initial

Precipitate Final

SH SH

DeVries, Stellacci, Science 315, 358, 2007


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Nano-Nylon Two-Phase TEM images

100 nm

NanoparticlesChains


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Chains of Big Particles


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AcknowledgementsGraduate StudentsRobert J . Barsotti, J r. ( now at

Arkema. Senior Scientist )Gretchen A. DeVriesAlicia M. J acksonA. Amy Yu ( also at MGH, post doc )

Tan Mau Wu

Benjamin WunschOsman Bakr (Harvard)Suelin Chen

J effrey KunaSarah ThevenetOzge Akbulut

J in Young KimHyewon Kim

J in-Mi J ung (KAIST)Ramona DallaPiccola (Trento)

Post-DocsMarkus Brunnbauer ( now at

Infineon, Senior Scientist )Xiaogang BrunoLiu ( now at NUS,

Assistant Professor )Brenda LongOktay Uzun

Ying YuAndrea CentroneAyush VermaKazuya NakataCedric DuboisGeorg Heimel

NSF: NER DMI-0303821NIRT DMR-0086944NIRT SCP-0304019CAREER

NIH TPEN ProgramHewlett PackardDeshpande Center

ACS-PRFReed Foundation at MITCMSE-MRSEC DMR 02-13282Int. Copper AssociationMARCO3M Non Tenured Faculty Award3M Innovation AwardDuPont Young Professor AwardPackard Foundation AwardMineral Technologies

CollaboratorsDavid Nelson, HarvardLucia Pasquato, TriesteRalph Weissleder, Harvard, MGHMolly Stevens, Imperial C., UK Henry I. Smith, MITEnzo diFrabrizio, Catanzaro, Italy

Anthony Guiseppe-Elie, C. VirginiaMaurizio Prato, TriesteMarcus Halik, Erlangen U., GermanyAnne Mayes, MITSharon Glotzer, U. Mich

J oerg Lahan, U. Mich.Nicola Marzari, MITDarrell Irvine, MITKrystyn Van Vliet, MITRobert Cohen, MIT

Undergraduates J acob M. Myerson ( now at MIT )Brian Netlner ( now at MIT )

Angela TongNishi N. Rochelle ( LSU, now at Purdue )Kathy Li ( now at UT Austin )Peter Stone ( now at Berkeley )Allon Houchbaum( now at Berkeley )Samantha Bennett ( now at Cambridge UK )

Tom Schilling ( will join Berkeley )Paulo Silva ( will join Northwestern )

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