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.