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Self Assembly July 22, 2009 Summer 2009 Nanotechnology Institute.

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Presentation on theme: "Self Assembly July 22, 2009 Summer 2009 Nanotechnology Institute."— Presentation transcript:

1 Self Assembly July 22, 2009 Summer 2009 Nanotechnology Institute

2 Making Nanostructures: Nanomanufacturing "Top down" versus "bottom up" methods Lithography Deposition Etching Machining Chemical Self-Assembly

3 What drives and governs self assembly? As you view the following images you should consider the question:

4 Tobacco Mosaic Virus

5 Gecko feet

6 Diatoms

7 Abalone

8 The Cell and Its Hierarchy

9 Whitesides et al. Science 295, 2418 (2002); Self assembly at all scales?




13 What drives self assembly? Static assembly (thermodynamic free energy minimum) -- once formed it is stable Dynamic assembly (kinetically formed, not necessarily thermodynamic minimum) -- not necessarily stable Forces of chemical bonding (4) covalent, ionic, van derWaals, hydrogen Other forces (magnetic, electrostatic, fluidic,...) Polar/Nonpolar (hydrophobicity) Shape (configurational) Templates (guided self assembly) Kinetic conditions (e.g., diffusion limited)

14 Excerpt from Letter of Benjamin Franklin to William Brownrigg (Nov. 7, 1773)...At length being at Clapham, where there is, on the Common, a large Pond... I fetched out a Cruet of Oil, and dropt a little of it on the Water. I saw it spread itself with surprising Swiftness upon the Surface... the Oil tho' not more than a Tea Spoonful... which spread amazingly, and extended itself gradually till it reached the Lee Side, making all that Quarter of the Pond, perhaps half an Acre, as smooth as a Looking Glass.... A nanofilm!

15 Langmuir Film pressure e.g., steric acid monolayer film water hydrophilic end hydrophobic end of an amphiphilic molecule

16 Langmuir-Blodgett Film Must control movable barrier to keep constant pressure multiple dips - multiple layers solid liquid

17 SAM: Self Assembled Monolayer Review article: J.C. Love, et al., Chem. Rev. 2005, 105, 1103 (G. Whitesides group, Chem Dept, Harvard) HS(CH 2 ) n X alkanethiol on gold (Au) where X is the end group of the chain –CH 3, –OH, or –COOH Longer alkanethiol molecules have greater thermodynamic stability

18 SAM: Self Assembled Monolayer Chemisorbed molecules Stabilized by intermolecular van der Waals interaction solid molecules from solution

19 SAMs on Nanoparticles J.C. Love, et al., Chem. Rev. 2005, 105, 1103 gold NP There are now many configurations and uses of SAMs imperfect packing

20 Nanoparticle Monolayer Formed at a Liquid-Air Interface

21 Nanoparticle Monolayer Formation Nature Materials MOVIE toluene Requirements: rapid evaporation excess dodecane present attractive interation to liq- air interface and between particles

22 SELF ASSEMBLY with DIBLOCK COPOLYMERS Block A Block B 10% A 30% A 50% A 70% A 90% A ~10 nm Ordered Phases PMMA PS Scale set by molecular size

23 CORE CONCEPT FOR NANOFABRICATION Deposition Template Etching Mask Nanoporous Membrane Remove polymer block within cylinders (expose and develop) Versatile, self-assembling, nanoscale lithographic system (physical or electrochemical)

24 Array Period = 24 nm Pore Diameter = 14 nm MW = 42,000 PS/PMMA TEMPLATE CHARACTERIZATION 100 cpp SEM SAXS

25 Improving Order: Guided Assembly in a Trench: Graphioepitaxy UMass-Seagate assemble here side view top view

26 nanoporous template Nanomagnets in a Self-Assembled Polymer Mask 1x10 12 magnets/in 2 Data Storage......and More

27 Metal Nanorings Ferromagnetic cobalt rings as small as 15 nm OD

28 Mohan Srinivasarao, et al. Science 292, 79 (2001). Kinetic Self-Assembly - by Breath Figures Polystyrene Film

29 More Fabrication by Breath Figures UMass: Alexander Böker, Yao Lin, Kristen Chiapperini, Reina Horowitz, Mike Thompson, Vincent Carreon, Ting Xu, Clarissa Abetz, Habib Skaff, A. D. Dinsmore, Todd Emrick and Thomas P. Russell, Nature Materials 3, (2004) a, Breath-figure pattern obtained with pure polystyrene. b, Optical and c, confocal fluorescence microscope images of different areas of a sample obtained from solvent-casting a polystyrene film from chloroform with CdSe nanoparticles. Scale bars: 16 mum. The inset in c shows a fluorescence intensity scan along the line indicated.

30 Anodized Aluminum Oxide Templates Aluminum Nanoporous aluminum oxide (AAO) ~ 40 V counter electrode Anodization Acid Bath I e.g., Keller, et al., J. Electrochem. Soc. 100, 411 (1953) Masuda & Fukuda, Science 268, 1466 (1995) (oxalic, sulfuric, or phosphoric acid) Masuda, et al.

31 Proposed AAO Growth Mechanism Figure adapted from Jessensky, Müller, & Gösele, Appl. Phys. Lett. 72, 1173 (1998) Al 2 O 3 E Al Al 3+ O 2- Density mismatch between Al and Al 2 O 3 Some Al 3+ goes to solution Mechanical stress yields pore growth in uniform hexagonal array Pore diameters of ~ nm possible by choice of anodization conditions

32 Improving AAO Order at Surface SiC stamp Aluminum anodize e.g., Masuda et al., Appl. Phys. Lett 71, 2770 (1997); Choi, et al., J. Vac. Sci. Tech. B 21, 763 (2003)

33 Ni in Anodized Aluminum Oxide Template SEM MFM Nielsch, et al. Appl. Phys. Lett. 79, 1360 (2001).

34 Large Scale Self-Assembly (Geological) Giant's Causeway (Northern Ireland) Volcanic basalt cooled rapidly to form these (mostly) hexagonally shaped columns

35 Microfluidic Assembly Application: RFID Alien Technology Nanoscale Phase Separation IBM "air gap" technology Introducing nanoscale air pockets into the insulating material separating wires on a computer chip -- lowers the capacitance flow direction Parts, having unique shape, are delivered via fluid flow to mating pockets on an assembly substrate.

36 Molecular Recognition ("lock and key" bonding) biotin-avidin pair (site-specific binding) thymine (T) adenine (A) guanine (G) cytosine (C) hydrogen bonding

37 Using Synthetic DNA for Designer Structures Ned Seeman, NYU Designer DNA molecules can be synthesized chemically, and allowed to assemble into a specific configuration of lowest energy.

38 Programmed DNA Folding to Make "DNA Origami" P.W.K. Rothemund, Nature 440, 297 (2006)

39 Additional examples to amplify concepts balls in a box magnets crystallization Forces (non-directional or directional), shape, thermal agitation Nanoscale self assembly coffee stain nanoparticle assembly by droplet others

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