Université Pierre et Marie Curie Paris 6 Two-dimensional Supramolecular Self-Assembling at Surfaces: Engineering and Functionality for Nanotechnologies (nanophotonics, nanooptoelectronics). André-Jean ATTIAS andre-jean.attias@upmc.fr
OUTLINE 1 – How to Shape Matter Macro vs Nanoworld 2 – Supramolecular chemistry at Surfaces Supramolecular chemistry Supramolecular chemistry at surfaces STM 3 – 2D Supramolecular Self-Assembly Hydrogen bond interaction Metal ligand interaction Van der Walls interaction 4- Our Contribution From Molecular ‘Clip’ to 3D Janus Tecton
How to Shape Matter? By carving To carve the four presidential heads into the face of Mount Rushmore, Borglum utilized new methods involving dynamite and pneumatic hammers to blast through a large amount of rock quickly, in addition to the more traditional tools of drills and chisels. Some 400 workers removed around 450,000 tons of rock from Mount Rushmore, which still remains in a heap near the base of the mountain.
How to Shape Matter? By carving To carve the four presidential heads into the face of Mount Rushmore, Borglum utilized new methods involving dynamite and pneumatic hammers to blast through a large amount of rock quickly, in addition to the more traditional tools of drills and chisels. Some 400 workers removed around 450,000 tons of rock from Mount Rushmore, which still remains in a heap near the base of the mountain.
How to Shape Matter? By assembling The entire project took about 23 years to complete, 2,300,000 building blocks , weighing an average of 2.5 tons each (Although some weigh as much as 16 tons) were used to build the great pyramid . The length of each side of the pyramid at the base is 755 feet (230.4 m). They rise at an angle of 51 52 ′ to a height, originally, of 481 feet (147 m) but nowadays 451 feet (138 m).
How to Control Matter at the Nanoscale? What is Nanotechnology? Nanotechnology is an emerging set of tools, techniques and unique applications involving the structure and composition of materials on a nanoscale. Nanotechnology aims to create and use structures, devices and systems in the size range of about 0.1–100 nm . (covering the atomic, molecular and macromolecular length scales). By manipulating matter at this length scale one hopes to achieve superior/new properties of these materials for applications in our macroscopic world. Miniaturization Semiconductor industry Emerging needs
How to Control Matter at the Nanoscale? µm - NANOTECHNOLOGY nm - • ‘top- down’: lithography and printing mature serial processes limited in sub-50 nm range J.V. Barth et al. Nature , 2005, 437, 671
How to Control Matter at the Nanoscale? Lithography • Extreme UV resolution • Electron-beam • X-ray radiation • Use of 193 excimer laser with phase shift masks to for features 65 nm in size. • Phase shift masks and complex optics are used to achieve this IBM Research resolution.
How to Control Matter at the Nanoscale?
How to Control Matter at the Nanoscale? Nanoimprint Lithography Soft and hard stamps are used to transfer patterns with feature sizes above 100 nm onto a wide range of substrates Photo Nanoimprint Lithography Thermoplastic Nanoimprint lithography http://www.semiconductoronline.com/Content/ProductShowcase/ http://www.nanonex.com/Picture/Resists2.jpg
How to Control Matter at the Nanoscale? Multiphoton lithography? ( talk by Prof. Kwang Sup Lee, Korea France joint Symposium ) http://www.cope.gatech.edu/rese Gold-plated helices written with arch/photoniccrystals.php 3D laser lithography courtesy What do you of Karlsruhe Institute of Technology (KIT), think? J. Gansel et al. http://polymer.hnu.kr/sub/sub02/sub_0201.jsp
Approaches to Nanofabrication µm - NANOTECHNOLOGY nm - • ‘top- down’: lithography and printing mature serial processes limited in sub-50 nm range • ‘bottom- up’: self -assembly molecular-level feature definition need of fundamental research J.V. Barth et al. Nature , 2005, 437, 671 new materials and functional systems
‘Bottom- up’ Strategy Instead of taking material away to make structures, the bottom-up approach selectively adds atoms/molecules to create structures. D = diffusion rate F = deposition flux When atoms/molecules are absorbed on substrate the type of growth is determined by the D/F ratio kinetic vs thermodynamic control in surface structuring Scale bar = 20 nm Diffusion limited regime Strain relaxation Molecular self-assembly Cu chains on Pd (110) Ge SC Qdots on Si(100) Benzoic acid Ag dendrites on Pt (111) BN nanomesh on Rh(111) based molecules @Ag (111) J.V. Barth et al. Nature , 2005, 437, 671
‘Bottom- up’ Strategy Molecular self-assembly at surfaces 1) Self-assembled monolayers (SAMs) SAMs provide a convenient, flexible, and simple system to tailor the interfacial properties of metals, metal oxides, and semiconductors. SAMs are organic assemblies formed by the adsorption of molecular constituents from solution or the gas phase onto the surface of solids The adsorbates organize spontaneously (and sometimes epitaxially) into crystalline (or semicrystalline) structures. The molecules that form SAMs have a chemical functionality, or “headgroup”, with a specific affinity for a substrate; The most extensively studied class of SAMs is derived from the adsorption of alkanethiols on gold
‘Bottom- up’ Strategy Molecular self-assembly at surfaces 1) Self-assembled monolayers (SAMs) George M. Whitesides et al. Chemical Revi ews, 2005, Vol. 105, No.4 SAMs are themselves nanostructures; the thickness of a SAM is typically 1-3 nm The composition of the molecular components of the SAM determines the atomic composition of the SAM perpendicular to the surface; this characteristic makes it possible to use organic synthesis to tailor organic and organometallic structures at the surface with positional control approaching0 .1 nm. They are easy to prepare, they can couple the external environment to the electronic and optical properties of metallic structures, they link molecular-level structures to macroscopic interfacial phenomena, such as wetting,adhesion, and friction.
‘Bottom- up’ Strategy Molecular self-assembly at surfaces 1) Self-assembled monolayers (SAMs) George M. Whitesides et al. Chemical Revi ews, 2005, Vol. 105, No.4 Drawback: No control of the lateral order
‘Bottom- up’ Strategy Molecular self-assembly at surfaces 2) Supramolecular Chemistry at Surfaces What is Supramolecular Chemistry ? “Chemistry of Molecular Assemblies and of the Intermolecular non- covalent Bond.” “Chemistry Beyond Molecule” Jean-Marie Lehn (Nobel prize, Chemistry, 1987) DNA: cooperative bonding Self-assembly
‘Bottom- up’ Strategy Molecular self-assembly at surfaces 2) Supramolecular Chemistry at Surfaces What is Supramolecular Chemistry ? Supramolecular chemistry focuses on the chemical systems made up of a discrete number of assembled molecular subunits or components. Forces controlling fabrication of molecular materials P. Samori, Qualitative comparison of the relevant length scales over which Angew. Chem. Int. Ed. 2007, 46, 4428 each type of force dominates the self-assembly.
‘Bottom- up’ Strategy Noncovalent synthesis: considerate use of weak intermolecular interactions to synthesize supermolecules with a high degree of structural complexity Molecular recognition: selective association of complementary functional molecular groups or a receptor and a guest species; Based on ‘lock-and- key’principle Tecton: derived from Greek τεκτων (builder), molecular building block programmed for the assembly of an architecture with specific spatial or functional features with carefully designed functional molecular building blocks, weak and selective noncovalent linkages program the formation of supramolecular architectures Hierarchical self-assembly
‘Bottom- up’ Strategy π -Conjugated Oligo-(p-phenylenevinylene) Rosettes and their Tubular Self-Assembly H-bonds in Nature E. W. Meijer Angew. Chem. Int. Ed . 2004, 43, 74 –78 Oligo( p -phenylenevinylene)s with pendant diamino triazine moieties can self-assemble through hydrogen-bonding interactions to give hexameric rosettes. H-bonding Representation of clockwise (CW) and counterclockwise (CCW) rosette structures showing the respective hydrogen-bonding patterns These rosettes further organize into large supramolecular tubules. 7 nm π - π interactions
OUTLINE 1 – How to Shape Matter Macro vs Nanoworld 2 – Supramolecular chemistry at Surfaces Supramolecular chemistry Supramolecular chemistry at surfaces STM 3 – 2D Supramolecular Self-Assembly Hydrogen bond interaction Metal ligand interaction Van der Walls interaction 4- Our Contribution From Molecular ‘Clip’ to 3D Janus Tecton
Engineering Nanostructures on Surfaces * Noncovalent synthesis in two dimensions: E rot 2D Supramolecular chemistry Mo Mole lecu cule le- Surfa face interactions E m Ad Adsor orpti tion on (E ad ) Therma mal migr grati tion on (E m ) E ad Rota otati tion onal moti otion on (E rot ot ) E as Mo Mole lecu cule le- Mo Mole lecu cule le lateral interactions Non on- cova ovalent bo bond nd for ormati tion on (Eas) -Hydrogen bonding -Metal-ligand interactions -Van der Waals interactions
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