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Self-Assembly Phenomena and Nanomaterials:
Uli Wiesner
Materials Science and Engineering
ubw1@cornell.edu
NSF NSEC Grantees Conference, Dec. 9-10, 2014
Present and Future
Cornell Graduate/Postdoc Students H. Arora, C. Burk, A. Burns, P. Boldrighini, M. Chavis, B.-K. Cho, C. Cowman, R. Dorin, J. Drewes, P. Du, D. Fayol, C. Garcia, Y. Gu, J. Gutmann, E. Herz, J. Hughes, K. Hur, S. Iyer, A. Jain, M. Kamperman, P. Kim, Y. Kim, R. Kogler, B. Lechesne, J. Lee, Z. Li, K. Ma, S. Mahajan, C. Orillal, H. Ow, R. Qi, T. Seetuwang, H. Sai, P. Simon, H. Sai, J. Song, R. Spencer, M. Stefik, Y. Sun, T. Swisher, K. Tan, S. Wang, S. Warren, L. Yeghiazarian, Y. Zhang
MPI-P Graduate/Postdoc Students D. Babski, S. De Paul, M. Langela H. Leist, D. Maring, S. Renker, V. Schaedler, M. Schoeps, M. Templin R. Ulrich, T. Volkmer, Y. Zhang
Funding Max Planck Society BASF DFG, BMBF Chrysalis biomat IBM Faculty Partnership MS&E Department Altria Group CCMR, CFCI, NBTC, General Motors NYS CAT Biotech Hercules
NSF, DOE, NIH, DHS, DOD (Army), DTRA KAUST-CU
Acknowledgements
Collaborators H. Spiess (MPI-P), A. Baiker (ETH Zurich) M. Elimilech (Yale), F. Escobedo (Cornell) B.K. Cho (Dankook, Korea), J. Lee (Pohang, Korea) E. Hoek (UCLA), G. Floudas (F.O.R.T.H.), S. Maier (Imperial, UK), R. Hennig (Cornell) M. Noginov (NSU), V.M. Shalaev (Purdue) T. Kuroda (Waseda, Jap.) J. Zwanziger (Dalhousie, Ca) M. Bradbury (MSKCC, NYC), H. Snaith (Oxford, UK) B. Baird (Cornell), G. Coates (Cornell), S. Nunes (KAUST) F. DiSalvo (Cornell), L. Fetters (Cornell), D. Muller (Cornell), S. Gruner (Cornell), U. Steiner (Cambridge, UK), M. Thompson (Cornell) W. Webb (Cornell), W. Zipfel (Cornell)
1987 Nobel Prize in Chemistry
Donald J. Cram Jean-Marie Lehn Charles J. Pedersen
Supramolecular chemistry: Chemistry beyond the covalent bond
Features of Self-Assembly (SA)
1.) Non-covalent, weak interactions
2.) Spontaneous & often far from equilibrium processes
5.) Ubiquitous in nature
3.) Time-, length-, and energy-scales may change during SA
4.) No universal theoretical description capturing all features
Self Assembled Monolayers: SAMs Example: Alkanethiolates on Au(111) lattice
- form of 2D self-assembly
- model systems to develop fundamental understanding of interfacial phenomena
- low cost organic alternative to MBE and CVD derived well-defined surfaces
- are of scientific as well as technological importance
R. G. Nuzzo et al., Chem. Rev. 105 (2005), 1103
Silicaceous sponge spicule Euplectella sponge
J. Aizenberg, D. Morse, P. Fratzl et al., Science 309, (2005), 275
500nm 1cm
5mm
1µm 5µm 10µm
100µm 20µm 25µm
The SA Toolbox: Nanoparticles
A. Burns, U.W., M. Bradbury et al., Nano Letters 9 (2009), 442
bladder
kidney
PEGs
C dot pegylation
< 10 nm C dots for efficient urinary excretion: “target or clear”
liver
bladder
Bradbury & Larson
mouse whole body
optical imaging
Cornell dots: fluorescent silica nanoparticles
systemic, i.v. injection in melanoma patients
M. Bradbury, U.W. et al., Science Trans. Med. 6 (2014), 260ra149
First Human Clinical Trial with Cornell dots First optical inorganic NPs approved as an investigational new drug
Peter L. Choyke (NCI) in same issue focus article: “ … a first of its kind in translation.” “…hope that we may soon see progress in the use of NPs in humans.”
J. S. Beck et al., Nature 359 (1992), 710.
N+Cl-
Surfactant micelle
Micellar Rod
Hexagonal array
Silicate
Silicate
Calcination
K. Kuroda et al., Bull. Chem. Soc. Jpn. 63 (1990), 988.
Ordered silica structures from surfactant SA Low molar mass surfactants as structure directing agents (SDAs)
Tailoring shape via branched architectures by epitaxial growth Inspiration: Tetrapods in semiconductor nanoparticles
A. Suteewong, U.W. et al., JACS. 133 (2011), 172 T. Suteewong, H. Sai, U.W. et al., Science 340 (2013), 337
P. Alivisatos et al. Nat. Mater. 2 (2003), 382 Y. Yin, P. Alivisatos, Nature 437 (2005), 664
E. V. Shevchenko, C. B. Murray et al., Nature 439 (2006), 55
Diversity of self-assembled binary NP superlattices
Colloidal SA
The SA Toolbox: Polymer Scaffolds
G. Fredrickson et al. Macromol. 39, 2449 (2006)
Block Copolymer Self-Assembly (BCP SA)
inorganic nanoparticles
From nanoparticles to functional materials
C. Orilall & U.W., Chem. Soc. Rev. 40 (2011), 520
inorganic nanoparticles
Merging polymer science with inorganic/solid-state chemistry
Templin, U.W. et al., Science 278 (1997), 1795
aluminosilicates high temperature non-oxides
Kamperman, U.W. et al., JACS 126 (2004), 14708
J. Gutmann Full Prof.
U. Duisburg- Essen, Germany
M. Kamperman Assist. Prof.
U. Wageningen, Netherlands
Thermodynamics of BCP SA: Entropy small particles larger particles
critical size < Ro
sparse
A. Balazs et al., Science 292 (2001), 2469
experimental results consistent with theory
dense
S. Warren, U.W. et al., Nat. Mater. 6 (2007), 156"provides opportunities beyond silica
S. Warren Ass. Prof.
UNC Chapel Hill
polycrystalline transition metal oxides
Lee, U.W. et al., Nat. Mater. 7 (2008), 222
20nm
polycrystalline metals
Warren, U.W. et al., Science 320 (2008), 1748"
Arora, Thompson, U.W. et al., Science 330 (2010), 214
single crystal semi- conductors & metals
J. Lee Ass. Prof. Postech South Korea
S. Warren Assist. Prof.
UNC Chapel Hill
H. Arora HGST
Non-equilibrium: Transient laser annealing High T-treatments of polymers on ns to ms time scales
Thompson
B. Jung, U.W., M. Thompson et al., ACS Nano 6 (2012), 5830.
Single crystal Si epitaxy in 100 nm BCP SA films ~100 nm porous oxide template final film after oxide removal HR-TEM
plan-view TEM and electron diffraction
H. Arora, U.W. et al., Science 330 (2010), 214"
DNA Origami: Programmed 2D SA Shapes
P. W. K. Rothmund, Nature 440 (2006), 297.
Self-Assembled Hierarchical Materials
H. Sai, U.W. et al., Science 341 (2013), 530
Elser, Estroff, Gruner & Muller
H. Sai
SIM2PLE: Spinodal-decomposition Induced Macro- and Mesophase separation PLus Extraction by rinsing
Hierarchical Self-Assembly made SIM2PLE
Science 341 (2013), 530
Our current level of understanding
Is “self-assembled materials by design” a reasonable promise ?
Z. Li Applied Materials
+
Z. Li, U.W. et al., Nat. Commun. 5 (2014), 3247
K. Hur, U.W. et al., J. Chem. Phys. 133 (2010), 19410 K. Hur, U.W. et al., Nano Letters 12 (2012), 3218
Escobedo & Hennig
1 Core simulation (Intel i7 CPU at 3.33 GHz)
K. Hur KIST, South Korea
Helmholtz Free Energy
Molecular Conformation Entropy
Short-range Enthalpic Interactions
Hard-sphere Interactions
Long-range Coulomb Interactions
The future: Are there emergent properties ?
- Optics: Self-assembled metamaterials
- Correlated electron systems: Self-assembled superconductors ?
Combining theory and experiment of self-assembled materials
SCFT + DFT for BCP/NP self-assembly
Hur, Escobedo, Hennig, U.W. et al., J. Chem. Phys. 133 (2010), 19410
Nano Letters 12 (2012), 3218
Theory-assisted design of BCP-metal NP hybrids
Li, Hur, U.W. et al.. Nat. Commun. 5 (2014), 3247"
Hur, Maier, Hennig, U.W. et al., Angew. Chem. 50 (2011), 11985
Negatic refractive index materials
Computational tools for mesoscale materials design
M Ψk(r) = ωk Ψk(r) Expt. vs Theory
a = 100 nm
K. Hur KIST, South Korea
Hennig & Maier
K. Hur, U.W. et al., Angew. Chem. Int. Ed. 50 (2011), 11985
positive refraction band: coupled plasmons
negative refraction band: circularly polarized light propagation
Angew. Chem. Int. Ed. 50 (2011), 11985
Baumberg & Steiner
S. Vignolini, K. Hur, U.W., U. Steiner et al., Adv. Mater. 24 (2012), OP23
+ etch + Au electrodep.
Comparison: exps. vs. FDTD simuations
K. Hur KIST, South Korea
M. Stefik Assist. Prof.
USC
BCP SA & The Arts
Mimicking nano structures of butterfly wings Structural colors from block copolymer self-assembly
Block copolymers meet the Arts Kimsooja’s “Needle Woman” on Cornell’s Arts & Sciences Quad.
Conclusions & Outlook
1.) Powerful design criteria are emerging for nanostructure control in self-assembled materials.
3.) Progress in theoretical description of self-assembled materials is made but this remains a grand challenge.
2.) Emerging areas in self-assembly include dynamically responsive nanomaterials and out of equilibrium nanostructure formation.
4.) Self-assembled nanomaterials are expected to have broad impact in areas ranging from microelectronics to energy generation & storage to optics.
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