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Physics and physical chemistry of micro- and nanotechnological systems Hans-Georg Braun Max Bergmann Center of Biomaterials Schedule WS 2010/2011 Topic A: Preparation and characterization of micro- and nanoscaled systems Topic B: Surface design Topic C: Liquids on surfaces and in microfluidic systems Topic D: Physical and strcutural principles for self-assembly on Varioous scales Topic E: Biomimetic inspired materials Micro- and Nanotechnology Molecular Molecular Separation Recognition Bioanalytics Diagnostics Bionano- technology Cell- / Micro- Biomimetic systems Chemistry Nanoobjects Layers Rods Particles z y x x y y 1-d 2-d 3-d < 100 nm History of nanotechnology Ultrathin gold layers ( 100 nm) History of nanotechnology Preparation of nanoobjects Faraday sols – 1864 Nanoparticle preparation History of nanotechnology Preparation of nanoobjects reduction (III) 0 HAu Cl4 Au Citrate Ascobic acid ~5 nm Faraday sols – 1864 Nanoparticle preparation 20 nm History of nanotechnology Analysis of nanoobjects Scattered light Nanoparticles Zsigmondy Ultramicroscope – 1900 Single particle observation History of nanotechnology Faraday’s „solutions“ are no real solutions (Tyndal Faraday effect) History of nanotechnology Physical properties of nanoobjects Einstein - Smoluchowski – 1905 Diffusion of nanoparticles History of nanotechnology Physical properties of nanoobjects Diffusion Einstein - Smoluchowki – 1905 Diffusion of nanoparticles Example: Cell free gene expression on a chip Buxboim and Bar-Ziv Small 3 (2007) 500 - 510 Micro- and nanostructures through self-assembly Hui Zhang and Mary J. Wirth* Anal. Chem.2005, 77,1237-1242 Micro- and nanostructures through lithographic approaches L. Jay Guo,*,† Xing Cheng,† and Chia-Fu Chou*,‡ NANO LETTERS 2004 Vol. 4, No. 1 69-73 Example: Microfluidic devices for protein crystallization Li and Ismagilov Annual Review on Biophysics 39 (2010) 139-158 Example: Microfluidic devices for protein crystallization Li and Ismagilov Annual Review on Biophysics 39 (2010) 139-158 Example: Open microfluid systems Franke and Wixforth ChemPhysChem 9 (2008) 2140-2156 Example: In-situ encapsulation of cells in micrenvironement Kaehr and Shear Lab on a chip 9 (2009) 2632 - 2637 2d structures 3d structures Lateral structures D D D D: lateral resolution D: lateral resolution H: height Aspect ratio α α = H/D Top down technologies for micro-/nanostructure preparation 100 µm 10 µm 1 µm 100 nm 10 nm 1 nm Sub-micrometer Optical Lithography Softlithography Ebeam Lithography AFM based Lithography Top down technologies for micro-/nanostructure preparation 2d,3d Electronbeam & Optical, X-ray Lithography, 2d,3d Soft-Lithography 2d AFM based Lithography (dip pen, SNOM,..) Ebeam and optical lithography Substrate Resist layer Irradiation Resist layer Positive resist Negative resist (becomes soluble upon irradiation) (becomes insoluble upon irradiation) Pattern transfer Film formation by spin coating Substrate Resist layer Inhomogeneous thickness of resist layer and time evolution of layer thickness Film formation by spin coating Process and materials parameter influencing film thickness • Solution viscosity • Solid content • Angular speed • Spin Time Wetting of (polymer) solutions on solid substrates ω ~ 0 deg. Spreading 0 < ω < 90 deg. Wetting ω > 90 deg. Non-wetting Wetting and dewetting of thin polymer (liquid films) on solid substrates Stability of thin films on surfaces 1) Stable film , 2) Unstable film 3) Metastable film Φ effective interface potential R. Seemann, S. Herminghaus, and K. Jacobs, PRL 86 (2001) 5534 Stability of thin films on surfaces R. Seemann, S. Herminghaus, and K. Jacobs, PRL 86 (2001) 5534 Stability of thin films on surfaces h Polymerfilm d SiO Si h: thickness of polymer film d: Thickness of SiO layer R. Seemann, S. Herminghaus, and K. Jacobs, PRL 86 (2001) 5534 Stability of thin films on surfaces on variable SiO interface R. Seemann, S. Herminghaus, and K. Jacobs, PRL 86 (2001) 5534 Wetting and partial wetting on surfaces G. Reiter et. Al. Langmuir 15 (1999) 2551 Optical lithography Thick layer resist technology : High aspect ratios Optical lithography Thick layer resist technology : Thick layer resist systems (SU-8) Optical lithography Thick layer resist technology : High aspect ratios I(d) H I(d) = I * exp- ε * d Inhomogeneous irradiation of polymer due to strong optical absorption (H > 100 µm) Optical lithography Chemically amplified negative resist T-BOC cleavage Acid catalyst negative resist Alkaline development Optical lithography Chemically amplified negative resist T-BOC cleavage Acid catalyst negative resist Alkaline development Optical lithography Light sources and structure resolution Hg KrF ArF F2 365 248 193 157 nm nm nm nm Optical lithography Lenses for KrF laser sources (248 nm) Structure resolution <180 nm Lense Material Calziumfluorid Optical Transmission high above 170 nm No birefringence Ebeam lithography Penetration depth of electrons with different energies in different materials Ebeam lithography Penetration depth of electrons with different energies Ebeam lithography Resolution down to 8 nm (A. Tilke LMU München) – Resist: Calixarene Optical lithography Two-photon lithography for complex 3d structures Optical lithography Two-photon lithography for complex 3d structures Optical lithography Two-photon lithography for complex 3d structures Optical lithography Two-photon lithography for complex 3d structures Optical lithography Quantum dots as 2 photon initiators 2 hν Cd o ( ) S o o o N.C. Strandwitz JACS 2008, 130(26), 8280-8288 Optical lithography in aqueous solutions Jhaveri, et. al. Chem. Mater. 2009, 21 (10), 2004 ff. Maskless optical lithography - A simple setup 100 µm lines 500 µm pitch Musgraves et. al. Am. J. Phys. 2005, 73 (10), 980 ff. Maskless optical lithography – 3d stereolithography Sun et. al. Sensors and Actuators A 121, 2005, 113 ff. Maskless optical lithography – 3d stereolithography Choi et. al. J. Mat. Process. Tech. 209, 2009, 5494 ff. Maskless optical lithography – 3d stereolithography Kidney scaffold Choi et. al. J. Mat. Process. Tech. 209, 2009, 5494 ff. DMD chip element Monk et. al. Microelectronic Eng., 27, 1995, 489 ff. Optical lithography in microfluidic systems Lee et. al. Lab Chip 9, 2009, 1670 ff. Optical lithography in microfluidic systems Chung et. al. Nature Materials 7, 2008, 581 ff. Optical lithography in µ-fluidic systems – Particle assembly Chung et. al. Nature Materials 7, 2008, 581 ff. Multi-LED array Grossmann et. al. J. Neural Eng., 11, 2010, 016004 ff. Multi-LED array Local stimulation of nerve cells Grossmann et. al. J. Neural Eng., 11, 2010, 016004 ff. Synchroton lithography / Synchroton X-rays Synchroton lithography X-rays Synchroton lithography / LIGA X-rays Synchroton lithography / Mask production X-rays Polymer embossing Embossing machine Process steps (Jenoptik) Cycle time ~ 7 minutes Heating of substrate and tools above Tg Application of pressure (~ kN) Cooling of substrate and embossing tool below Tg Removal of tool Polymer embossing Silicon master embossing tool Polymer replica made by embossing Polymer microysystems Lensarrays Beam splitter Microdropdeposition Polydimethylsiloxane (PDMS) - The material - Me : - CH3 Pt Curing Crosslinking Linear flexible polymer Flexible crosslinked (liquid @RT) Rubber ( @RT) Polydimethylsiloxane (PDMS) - The material Chemical crosslinking by hydrosilylation Schmid,H. Macromolecules 33, 3042 (2000) Polydimethylsiloxane (PDMS) - The material Chemical modification by hydrosilylation (-O-CH2-CH2)- EO Hydrophilic Polydimethylsiloxane (PDMS) - The material Jessamine Ng Lee, Cheolmin Park,† and George M. Whitesides* Anal. Chem.2003, 75,6544-6554 Polydimethylsiloxane (PDMS) - The material T.R.E. Simpsona, Z. Tabatabaianb, C. Jeynesb, B. Parbhooc, and J.L. Keddiea* Polydimethylsiloxane (PDMS) - The material Hydrophilization by surface plasma treatment O. Steinbock, Langmuir 19, 8117 (2003) Liquid filling of a capillary by Surface interactions S. Stark,Microelectronic Eng. 67/68, 229 (2003) Liquid filling of a capillary by Surface interactions S. Stark,Microelectronic Eng. 67/68, 229 (2003) Polydimethylsiloxane (PDMS) - The material Hydrophilization by surface plasma treatment O. Steinbock, Langmuir 19, 8117 (2003) Polydimethylsiloxane (PDMS) - The material Hydrophilization by surface plasma treatment Hydrophobic recovery measured by surcface force AFM M. Meincken, T.A. Berhane, P.E. Mallon, Polymer 46 (2005) 203–208 Polydimethylsiloxane (PDMS) - The material Compression mold 2 N/mm2 Compression mold 9.7 N/mm2 Schmid,H. Macromolecules 33, 3042 (2000) Permeation induced flow in PDMS channels P. Silberzan, Europhys. Letters 68, 412 (2004) Permeation induced flow in PDMS channels P. Silberzan, Europhys. Letters 68, 412 (2004) Permeation induced flow in PDMS channels P. Silberzan, Europhys. Letters 68, 412 (2004) PDMS based complex microfluidic systems Multilayer µ-fluidic systems a) Fluidic transport layer b) Control layer S. Quake,Science 298, 580 (2002) TIRF measurement of particle velocity near surfaces K.Breuer 2003 ASME International Mechanical Engineering Congress & Exposition Washington, D.C., November 16-21, 2003 TIRF measurement of particle velocity near surfaces K.Breuer 2003 ASME International Mechanical Engineering Congress & Exposition Washington, D.C., November 16-21, 2003 Unconventional lithographic techniques Unconventional lithographic techniques Softlithographic techniques Se-Jin Choi,† Pil J. Yoo,‡ Seung J. Baek,† Tae W. Kim,† and Hong H. Lee*,‡ - J. AM. CHEM. SOC. 2004, 126, 7744 7745 Softlithographic