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Thomas E. MalloukDepartment of Chemistry, The Pennsylvania State University
Foresight Conference Tutorial, November 2, 2000
Nanomaterials: Synthesis and Assembly
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Inorganic nanomaterials have interesting physical properties
NR4+
OH-
H2La2Ti3O10
High dielectricmetal oxide“scrolls”
R. E. Schaak, et al.Chem. Mater. 2000
Superparamagnetic 6 nm FePt cubes
S. Sun, C. B. Murray, D. Weller, L. Folks,A. Moser, Science 2000, 287, 1989.
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Special Properties of Nanomaterials
High surface/bulk ratio• Catalysis• Nanoparticle reagents• Heat dissipation• Laminar flow
Finite size effects• Quantum confinement• Interparticle tunneling• Proximity effects• High probability of defect- free crystals
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CdSe/CdS core-shell particlesExcitons confined to core
Defect-free nanocrystalshigh fluorescence quantum yield
A. P. Alivisatos et al., Science 1998, 281, 2013.
Dual fluorescencelabeling of actinfilaments and fibroblasts
2.1 - 4.6 nm
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Dissolution and Melting of Nanoparticles
Solubility increases and melting point decreases for nanoparticles
Ostwald-Freundlich relationship
S = S0 expγslV
RTdP
S/S
0
Particle Diameter (nm)
100
102
104
106
108
1010
1012
1 10 100 1000
γsl = 0.9 N/m
Au nanocrystal opalsLarge particles grow at
the expense of small ones
J. R. Heath, Lamgmuir 1996
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Motivation for studying inorganic nanomaterials: Functional nanoscale assemblies
• Electronics• Robotics • Solar Energy Conversion• Nano-Batteries and Fuel Cells• Separations and Analysis• Photonics
Intricate, non-periodic structures
Sub-lithographic length scale
Inorganic materials properties
Lessons from biology
•Molecularly precise building units with asymmetric shapes: α-helices, beta sheets, nucleic acid duplexes and loops
•Recognition is non-covalent, highly shape-dependent:4-helix bundles, DNA-protein, ribosome-RNA complexes
•Hierarchical assembly to imprecise functional units:membranes, chromosomes, cells, organs, people
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5 µm
860 nm silica opalthin film
Colloidal crystalsInteresting for applications in optics, sensors, separations
So far, building blocks are spheres and high symmetry polyhedra limited structural variety
polymer“inverse opal”
Pt inverse opal with12 nm “necks”
Johnson, et al.,Science 1999,283, 963.
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“Cookie cutter” fabrication of mm scale shapes
Assembly at a planar interface•Hexagons confined to a plane for 2D assembly•Agitated in interfacial plane to bring hexagons into contact
Poly(dimethylsiloxane) (PDMS)• hydrophobic (OSiMe2)• hydrophilic in O2 plasma
5.4 mm
1-2 mm
Bowden, N.; Terfort, A.; Carbeck, J.; Whitesides, G. M. Science 1997, 276, 233.
Particle Assembly - Proof of ConceptNon-covalent assembly of asymmetric polygons
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H2O(p=1.00 g/cm3)
Perfluorodecalin (PFD)(p=1.91 g/cm3)
PDMS hexagon(p=1.05 g/cm3)hydrophilic
hydrophobic
1-2 Hz Negative meniscus (hydrophilic edges)
Positive meniscus (hydrophobic edges)
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Linear chain formation - [1,4] hexagons
Bowden, N.; Choi, I. S.; Grzybowski, B. A.; Whitesides, G. M. J. Am. Chem. Soc. 1999, 121, 5373.
Trimer formation - [1,2] hexagons
tilted [1,2]hexagon
Trimers(thermodynamic
assembly)
Trimer superlattice(slower rotation speed,less stable interactions)
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hexane
water
Terfort, A.; Bowden, N.; Whitesides, G. M. Nature 1997, 386, 162.Huck, W. T. S.; Tien, J.; Whitesides, G. M. J. Am. Chem. Soc. 1998, 120, 8267.
Self assembly of millimeter-scale 3-D objects
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Self-assembly of 3-Dcircuits from millimeter-scale components
• Series or parallel wiring• Circuit connectivity is programmed by asymmetry of building blocks
D. H. Gracias, J. Tien, T. L. Breen, C. Hsu,G. M. Whitesides, Science 2000, 289, 1170.
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Key questions for nanoscale assembly
•Synthetic techniques for asymmetric objects
Bottom up (molecule precise) or cookie cutter (top down)?
What is the minimal tool kit (balls, polygons, rods, helices…)?
•Assembly issues
Proof of concept with small systems (dimers, host guest complexes, linear arrays)
Combine small scale assembly with lithographic patterning
What does the nanoparticle toolbox look like now?
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Faceted CdSe (wurzite)nanocrystal (A. P. Alivisatos)
Pt nano-cubes (M. A. El-Sayed)
Synthesis of non-spherical nanoparticles
• Uniformity is hard to achieve (but improving!)
• Symmetry is still too high for shape-directed assembly
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Cd
Se
CdSe Nanorods and “Arrowheads”
L. Manna, E. C. Scher, A. P. Alivisatos, JACS 2000 (in press).
• Nanocrystal habit controlled by surfactant composition
• Multiple injection/growth cycles develop specific crystal faces
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CdSe Tetrapods
L. Manna, E. C. Scher, A. P. Alivisatos, JACS 2000 (in press).
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Two-Dimensional BuildingBlocks from Inorganic Solids
(C4H9)4N+OH-
dil. HCl
α-Zr(HOPO3)2 . H2Od(001) = 7.6 Å Colloid of single layers
TBA+
TBA+
intercalated solidd(001) = 16.5Å
TBA+
TBA+
excess(C4H9)4N+OH-
K4Nb6O17 H2K2Nb6O17
excess(C4H9)4N+OH-
TBA+TBA+
TBA+TBA+
Colloid of double layers
TBA+
TBA+
TBA+
TBA+
TBA+TBA+
H2OH2O
H2O
H2O
Nanoscale sheets from lamellar precursor solids
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TEM of 1.5 nm thickTBA0.17H0.83Ca2Nb3O10sheets
TBA0.17H0.83Ca2Nb3O10sheets tile densely on aSi/polycation (PDDA)surface
AFM Image
Exfoliated sheets are crystalline and exactly1 molecule thick, but are irregularly shaped
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Sequential Anion-Cation Adsorption
(3)oligo- or
polycation
(2), (3), etc. multilayerthin film
substrate(Si, Au, ...)
3
H2N(CH2)2SH
H2N(CH2)4 Si CHOCH
CH3
3(1)
++
+ +++
++++
+++
++
TBA+
TBA+
- --
-
-
exfoliated
α-ZrP, K2Nb6O172- , etc.
(2)
TBA+ TBA+TBA+
- - - -
-+
+++++
++
++++
+
+
++
+
+
+
- --
-
-+++ +
+++
+++
+
++
Molecular 'Beaker' Epitaxy
S. W. Keller et al., J. Am. Chem. Soc. 1994, 116, 8817.E. R. Kleinfeld, G. L. Ferguson Science 1994, 265, 370.
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0 6 µm
5 nm
0Silicon
α-ZrP
PVT-MV2+
HTiNbO5
Amine
Layer-by-layer assembly of irregular sheets
Structure is well controlled in stacking directions
No control in the horizontal directions
Complex stacking sequences are accessible
Large variety of inorganic and organic building blocks
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Inorganic Layer
Inorganic Layer
Electron Acceptore-
Substrate
Pd
Pd
ENERGYTRANSFER
N
N
N
N Pd
R' R'
R' R'
PdTSPP4-: R' = SO3-
PdTAPP4+: R' = NMe3+
λa = 424, 520λe = 720
(CH2 CH)y
NH3+Cl-
(CH2 CH)x
NHR
PAH: R = H
COO-
OHHO
+
C-NH
=
S
Fl-PAH: R =
Coum-PAH: R =
CO
O O NEt2
λa = 418
λe = 485 λa = 500
λe = 530
CH2 CH3N N+ +
CH)0.44(CH2
CH3
CH)0.39(CH2CH)0.17(CH2
CH2Br
HTiNbO5
α-Zr(HPO4)2
Multi-step energy/electron transfer cascades
• Densely tiled sheets separate redox polymer layers by 1 nm
• Light-driven 4-step energy/electron transfer sequence with >60% quantum yield
D. M. Kaschak et al., J. Am. Chem. Soc. 1999, 121, 3435.
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Aulonia hexagona
spheroidal hexagonalnetwork skeleton
Biomimetic materials synthesis
Macromolecular templatingMorphogenesis
This is not made by assemblingpolygons around a droplet!
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Natural discoid silicates
G. A. Ozin, Acc. Chem. Res. 1997, 30, 17.
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• 1-D or 3-D pore network• Template (surfactant or block copolymer) directs structure
MesoporousMolecularSieves
+
+
+
+
+ +
+
++
+
+ surfactant
cationicmicelle
+
+
+
+
+ +
+
++
+
++
+
+
+ +
+
++
+
+
+
+
+
+ +
+
++
+
+
+
+
+
+ +
+
++
+
++
+
++ +
+
+ +
+
+
+
+
+
+ +
+
++
+
++
+
++ +
+
+ +
+
++
+
++ +
+
+ +
+
++
+
+
+ +
+
++
+
+
+
+
++ +
+
++
+
anionic silicate
hydrothermalcrystallization
burn outtemplate
mesoporous silicate
7 nm diaPt replica
wires
SBA-15
G. Stucky, et al., Chem. Mater. 2000, 12, 2069
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G. A. Ozin, Acc. Chem. Res. 1997, 30, 17.
Biomimetic porous silicates
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Controlling the Morphology ofMesoporous Materials
Thin Films and “Onions”
C. J. Brinker, et al.Adv. Mater. 1999,11, 579.
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Discoids, fibers, spheres, open spirals
•Silicate crystallization around lyotropic templates
•Nucleation, polymerization, differential contraction
control shape evolution
G. A. Ozin, Can. J. Chem. 1999
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hybridize
DNA Base Pairing
Highly specific bindingTemperature, sequence reversibility
A.P. Alivisatos et al., Nature 382, 609 (1996)C.A. Mirkin et al., Nature 382, 607 (1996)
N. Seeman, Acc. Chem. Res. 30, 357 (1997).
Asymmetric glue for symmetric nanoparticles
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Oligonucleotide linking of nanoparticles
Change in plasmon absorbance band is a litmus test for a specific polynucleotide target
C. A. Mirkin, et al., Science 1997, 277, 1078.
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100 nm
25 nm
20 nm
nS
O OS
Sn
S
O
O
S
O
n
n
OSC4
L. C. Brousseau III, J. P. Novak, D.L. Feldheim(North Carolina State University)
Linker-controlled formation of nanoparticle dimers, trimers, and tetramers
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Building complex structures from symmetric objects
• Function block approach
Substrate patterns impose order on self-assembled nanostructures
Control of nanoscale arrangment by lithographic scale patterning
8
8
+
Self-assembling nanoscale objects “Nano-frame” Regular function block
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Younan Xia, U. of Washington
Sphere assembly driven by capillary forces
• Dimensions of holes and spheres determine packing arrangement• Flow controls orientation of spheres
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Younan Xia, U. of Washington
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Younan Xia, U. of Washington
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TEM
Younan Xia, U. of Washington
Synthesis of asymmetric bead dimers