TheSupramolecularNanoMaterialsGroup

From Nano-Particles to Nano-Polymers

Francesco Stellacci
Department of Materials Science and Engineering, MIT frstella@mit.edu

The Supramolecular NanoMaterials Group

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Monolayer Protected Metal Nanoparticles

Functionalized Carbon Nanotubes Nanowires

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

NANO-MATERIALS
Jackson, Myerson, Stellacci, Nat. Mat., 3, 330, 2004 Akthakul, Stellacci, Mayes,. Adv. Mat., 17, 532, 2005 Jackson, Silva, Hu, Stellacci, JACS., 128, 11135, 2006 DeVries, Brunnbauer, Stellacci, Science 315, 358, 2007 Centrone, Yu, Stellacci,Small, 3, 814, 2007

20 m
Wunsch, Stellacci, Prato, manuscript in prep Long, Wu, Wunsch, Marzari, Stellacci in prep.. Liu, Yuan, Kong, Stellacci manuscript in prep.

Supramolecular Lithography

Supramolecular Materials Science

LITHOGRAPHY

Supramolecular Nano Stamping

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

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

Metal Nanoparticles Synthesis

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Metal Salt (AuHCl4) +

HS

+
HS

Reducing Agent (NaBH4)

HS

HS

Direct mixed ligands reaction**

Ligand exchange reaction*

HS

HS

F. Stellacci, et al. Adv. Mat. 2002, 14, 194

A. C. Templeton, M. P. Wuelfing and R. W. Mu rray, Accounts Chem. Res. 2000, 33, 27

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

1 = (1 + 2 m )2 + 22
m is a volume-average of the dielectric constants () of the ligand molecules and the solvent
Conjugated molecules:
NH2

gold

NO2 O OH

SH
4-Aminophenyldisulfide

SH

SH
SH Dimethyl (4,4 dithiobiscinnamate)

4-Fluorobenzenethiol 5,5-Dithiobis(2-nitrobenzoic acid)

(APS)
Electron donor

(FBT)
Electron acceptor

(NBA)
Electron acceptor

(CIN)
Electron acceptor

Absorption by Functionalized Nanoparticles

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Absorption spectra for fully conjugated nanoparticles

0.4

By Mie theory: CIN

Absorption

0.35 0.3 0.25 0.2 0.15 0.1

Spectra taken in dichlorobenzene (DCB)

541

*
O O

Aminophenyldisulfide Fluorobenzenethiol Nitrobenzoic acid Cinnamate

530

SH

FBT APS (NBA)

Increasing

522
SH

NH2

NO2 O OH

510

SH

0.05 0 300 400

SH

500

600
Wavelength (nm)

700

800

Trend in predicted by polarizability of molecules Steric hindrance of NBA molecule causes porous ligand shell, effectively lowering relative to expected value
* Chromophore absorption from ligands; unrelated to plasmon resonance

Increasingly Conjugated Nanoparticles

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Absorption spectra for increasingly conjugated FBT series nanoparticles

0.6

Spectra taken in dichlorobenzene (DCB)

528

0.5

hexanethiol 1:2 1:1 2:1 conjugated

Nanoparticles with varying ratios of:

HS

Absorption

0.4

522 522 518

More FBT Increasing

(low )
F

HT
and

0.3

518

FBT
SH

0.2

eff
350

V + VFBT FBT = HT HT Vligands

450 550
Wavelength (nm)

(high )

0.1 250 650 750 850

Larger fractions of conjugated FBT make ligand shell more polarizable; demonstrates corresponding increase Similar trends are observed in other molecule series as well

Characterizing Metal Nanoparticles

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3 nm

TEM shows atoms in the core

STM shows ligands in the shell

2.7 nm

Homoligand particles ligand structure

S
D/2 x d/2

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

S S/D = x/d

Assumptions: The nanoparticle can be approximated as a sphere Ligand 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 Based on Luedtke and Landman Faraday Discussions 2004, 125, 1-22

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

Octanethiol (C8) homoligand np

Diameter =7.422nm Ligand length= 1.08 nm Average STM observed headgroup spacing <S> = 0.5
1.9nm

Dodecanethiol (C12) homoligand np

Diameter=7.418 Ligand length=1.56 nm Average STM observed headgroup spacing <S>= 0.6305

Average S-S spacing <x>=0.409 nm

Average S-S spacing <x>=0.3646 nm

Mixed Self-Assembled Monolayers

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Au (111)

Randomly distributed domains of OT form in a surrounding matrix of MPA

MPA
HS COOH HS

5 nm

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.

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

STM Images of Rippled Nanoparticles

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bb

5 nm
b a

2 nm
c

2 nm

2 nm

c
HS COOH

MPA
HS

5 nm

OT

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

Hydrophobic/Hydrophilic Ripples
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5 nm
b a c

2 nm

2 nm

5 nm

STM imaging of Nanoparticles

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2 2
2

Average Spacing (nm Average Spacing (nm Average Spacing (nm) (nm Average Spacing ) ))) Average Spacing (nm

1.8 2 1.8
1.8 1.6 1.4 1.2 1

1.8 1.6 1.6 1.6 1.4 1.4 1.4 1.2 1.2 1.2 1 1

Noise

OT:MPA 2:1

1 0.8 0.8

OT:MPA 1:1 OT:MPA 30:1

0.8

0.8

0.6 0.6 0.6 0.6 0.4 0.4 0.4 0.4 0.2 0.2 0.2 0.2

5 nm

Au foil hemispheres

0 0 0 0 0 0 0 0

0.1 0.1 0.1 0.1

0.2 0.2 0.2

0.3 0.3 0.3 0.3

0.4 1.2 0.4 0.5 0.6 0.7 0.8 0.9 1 1.1 1.2 0.4 0.5 0.5 0.6 0.6 0.7 0.7 0.8 0.8 0.9 0.9 1 0.4 0.5 0.6 0.7 0.8 0.9 1 1 1.1 1.11.1 1.2 1.2

STM height image of OT:MPA 2:1 gold nanoparticles on gold foil

Imaging Speed Speed (m/s (m/s) ) Imaging Imaging Speed (m/s ) Imaging Speed (m/s )

Noise and Ripples

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005 image taken at 0.57 m/s Shows average ripple spacing of 0.699 nm 0.098 nm

007 image taken at 0.814 m/s Shows average ripple spacing of 0.743 nm 0.052 nm
ajs6_11_12

1.496 m/s

5 nm

1.595m/s

5 nm

1.841 m/s

5 nm

b
noise spacing [nm]

1.8 1.6 1.4

c
ripple spacing [nm]

1.8 1.6 1.4 1.2 1.0 0.8 0.6 0.4 0.2

ripple spacing [nm]

1.8 1.6 1.4 1.2 1.0 0.8 0.6 0.4 0.2

1.2 1.0 0.8 0.6 0.4 0.2 0.0 0.5 1.0 1.5 speed [um/s] 2.0

1 Ripple Spacing [nm] 0.9 0.8 0.7 0.6 0.5 0.4 4 4.5 5 5.5 6 6.5 7 7.5 8

.007 .007' .007'' .005 .005' .005''

2.5

0.0 0.5

1.0

1.5 speed [um/s]

2.0

2.5

0.0 0.5

1.0

1.5 speed [um/s]

2.0

2.5

8.5

9.5

10
Jackson, Silva, Hu, Stellacci, JACS., 128, 11135, 2006

Diameter [nm]

Phase Separation on Nanoparticles

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HS

HS

NH 2

Hexanethiol: p-Aminothiophenol Ag/-SH or /-NH2, Fe3O4 /-COOH, CaCO3/COOH

OT:MPA
O
HS
OH

HS

OH

OT:Mercaptohexanol
HS HS

OT:MUA

Curvature Effects
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OT:MPA Mixed Monolayers formed on surfaces of varying curvatures

Increasing Curvature

10 nm

10 nm

5 nm

5 nm

Flat Au (111) on Mica

Au on Si, with 20 nm hemispheres

Au film with Au crystals ~ 10 nm

Au film with Au crystals ~ 4 nm

The Hairy Ball Theorem and SAMs

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Self-Assembled Monolayers

The hairy ball theorem

One Vector Two Vectors

Molecules in SAMs form a 2D crystal, that is a vectorial order.
The hairy ball theorem states that a vectorial order cannot propagate on a topological sphere unless the vector assumes a zero value in at least two points, called poles.

*Poincarre, J. Math. Pure Appl. 1, 167, 1885; Nelson, Nano Lett., 2, 1125, 2002;

DeVries, Science 315, 358, 2007; see also Zerbetto et al. Small, 2007

Thermodynamic interpretation
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What is the Vectorial Order in SAMs?

What is a topological sphere?

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

Molecules in SAMs form a specific angle with the surface normal in order to maximize van derWaals interactions. One can define a vector (from the attachment point to the projection of the molecular head group) to describe the molecular position.

dodecane solution solution

HS

HS

HS

Chemistry of chain formation

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

SH

SH

Short reaction times allow functionalization only at the polar singularities

HOOC SH

O HO

HS

SH

O OH

2. Two-phase reaction: interface-controlled stoichiometry

Nanoparticles in toluene phase 1,6-Diaminohexane in water phase
H2N NH2

Amide bonds

Nano-nylon

Precipitation at the toluene-water interface indicates the formation of insoluble material

Initial

Precipitate
DeVries, Stellacci, Science 315, 358, 2007

Final

Nano-Nylon Two-Phase TEM images

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Nanoparticles Chains

100 nm

Inter-Particle Distance
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Potential linker position

Measured interparticle distance

Potential EGDA linker conformation

O HS

O N H O N H O N H O

5
O

SH

DAH theoretical length = 3.6 nm

SH

HS

N H

EGDA theoretical length = 9.6 nm

Chains of Big Particles

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Acknowledgements
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Graduate Students Robert J. Barsotti, Jr. (now at Arkema. Senior Scientist) Gretchen A. DeVries Alicia M. Jackson A. Amy Yu (also at MGH, post doc) Tan Mau Wu Benjamin Wunsch Osman Bakr (Harvard) Suelin Chen Jeffrey Kuna Sarah Thevenet Ozge Akbulut Jin Young Kim Hyewon Kim Jin-Mi Jung (KAIST) Ramona DallaPiccola (Trento) Post-Docs Markus Brunnbauer (now at Infineon, Senior Scientist) Xiaogang Bruno Liu (now at NUS, Assistant Professor) Brenda Long Oktay Uzun Ying Yu Andrea Centrone Ayush Verma Kazuya Nakata Cedric Dubois Georg Heimel

Collaborators David Nelson, Harvard Lucia Pasquato, Trieste Ralph Weissleder, Harvard, MGH Molly Stevens, Imperial C., UK Henry I. Smith, MIT Enzo diFrabrizio, Catanzaro, Italy Anthony Guiseppe-Elie, C. Virginia Maurizio Prato, Trieste Marcus Halik, Erlangen U., Germany Anne Mayes, MIT Sharon Glotzer, U. Mich Joerg Lahan, U. Mich. Nicola Marzari, MIT Darrell Irvine, MIT Krystyn Van Vliet, MIT Robert Cohen, MIT Undergraduates Jacob M. Myerson ( now at MIT) Brian Netlner ( now at MIT) Angela Tong Nishi 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)

NSF:

NER DMI-0303821 NIRT DMR-0086944 NIRT SCP-0304019 CAREER NIH TPEN Program Hewlett Packard Deshpande Center ACS-PRF Reed Foundation at MIT CMSE-MRSEC DMR 02-13282 Int. Copper Association MARCO 3M Non Tenured Faculty Award 3M Innovation Award DuPont Young Professor Award Packard Foundation Award Mineral Technologies