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Francesco Stella CC I
Francesco Stella CC I
Francesco Stella CC I
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
LITHOGRAPHY
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
HS
+
HS
HS
HS
Nanoparticle Absorption
S u N M a G
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)
(APS)
Electron donor
(FBT)
Electron acceptor
(NBA)
Electron acceptor
(CIN)
Electron acceptor
541
*
O O
530
SH
522
SH
NH2
NO2 O OH
510
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
528
0.5
Absorption
0.4
(low )
F
HT
and
0.3
518
FBT
SH
0.2
eff
350
(high )
Larger fractions of conjugated FBT make ligand shell more polarizable; demonstrates corresponding increase Similar trends are observed in other molecule series as well
3 nm
2.7 nm
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
Au (111)
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.
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
S u N M a G
5 nm
b a c
2 nm
2 nm
5 nm
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
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
0.4 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
Imaging Speed Speed (m/s (m/s) ) Imaging Imaging Speed (m/s ) Imaging Speed (m/s )
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]
c
ripple spacing [nm]
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
2.5
0.0 0.5
1.0
2.0
2.5
0.0 0.5
1.0
2.0
2.5
8.5
9.5
10
Jackson, Silva, Hu, Stellacci, JACS., 128, 11135, 2006
Diameter [nm]
HS
HS
NH 2
OT:MPA
O
HS
OH
HS
OH
OT:Mercaptohexanol
HS HS
OT:MUA
Curvature Effects
S u N M a G
10 nm
10 nm
5 nm
5 nm
Self-Assembled Monolayers
*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
S u N M a G
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.
HS
HS
SH
O HO
HS
SH
O OH
Amide bonds
Nano-nylon
Initial
Precipitate
DeVries, Stellacci, Science 315, 358, 2007
Final
Nanoparticles Chains
100 nm
Inter-Particle Distance
S u N M a G
O HS
O N H O N H O N H O
5
O
SH
HS
N H
Acknowledgements
S u N M a G
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