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Polymers and biopolymers in micro- and nanotechnology
What are micro- and nanotechnology about ?
• Majour goals • Representative examples from microtechnology• Representative examples from nanotechnology
What are the materials used in micro- and nanotechnology?
• Silicon, metals, semiconductors and inorganics• Polymers, organic materials
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Polymers and biopolymers in micro- and nanotechnology
What are the technologies used in micro- and nanosciences?
• Structuring technologies• Analytical techniques• Self assembly
What is the biological input to micro- and nanotechnology?
• Biomimetic strategies• Biophysical techniques
What are the visionary goals of nanotechnology ?
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History of nanotechnology
Ultrathin gold layers ( 100 nm)
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History of nanotechnology
Technological applications of nanoobjects
Colloidal colours in glases –Optical properties of nanoparticles
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History of nanotechnologyDie herrliche rote Farbe der kolloiden Goldlösung hat die Technik schon seit vielen Jahrhunderten im Goldrubinglas benutzt, das, wie Zsigmondy und Siedentopf mit Hilfe des Ultramikroskops bewiesen haben, feste Teilchen metallischen Goldes als färbende Substanz enthält (im Ultramikroskop erscheinen diese Goldteilchen als grünglänzende Scheibchen). Man stellt das echte Rubinglas her, indem man zur Glasmasse Chlorgold zufügt. Bei rascherem Abkühlen erhalt man ein farb-loses Glas; erhitzt man von neuem, bis das Glas erweicht, so läuft es plötzlich prachtvoll rubinrot an. Schlechtes Rubinglas dagegen wird beim Wiedererhitzen blau, violett und rosa; das Ultramikroskop zeigt hier viel hellere und viel weiter voneinander entfernte Teilchen, die im blauen Glase kupferrot, im violetten Glase gelb und dort, wo das Glas rosa ist, grün glänzen.Die Bedeutung der Kolloide für die TechnikK. Arndt in Kolloid Zeitschrift S. 1 (1909)
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History of nanotechnology
Justus Liebig: 1843 Preparation of silver mirrors
Michael Farady: 1856 Preparation of ultrathin layers
Observation of red „gold solutions“ as by product
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History of nanotechnology
Analysis of nanoobjects
Zsigmondy Ultramicroscope – 1900Single particle observation
Scattered light
Nanoparticles
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History of nanotechnology
Faraday’s „solutions“ are no real solutions(Tyndal Faraday effect)
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History of nanotechnology
Physical properties of nanoobjects
Einstein - Smoluchowki – 1905Diffusion of nanoparticles
Diffusion
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Making money with nanotechnology
Au Sol particles (6 nm) : 25 ml , 0.01 % HAuCl4 : 92 €Au 1 Oz : ......
Au 1 Oz : 400 €
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Science Fiction ?Lets build a small world
Complex structures of a small world
/ 10 7 / 10 8
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Polymers and nanotechnologyConformation and size of single macromolcules
Freely jointed chain (Frei drehbare Kette):
(Valenzwinkelkette)
(Valenzwinkelkette mit gehinderter Rotation)
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Micro- and nanostructures through lithographic approaches
L. Jay Guo,*,† Xing Cheng,† and Chia-Fu Chou*,‡
NANO LETTERS 2004 Vol. 4, No. 1 69-73
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Polymers and nanotechnology
Polymer coil
Nanoparticle Carbonnanotube
Polymer rod
5 nm – 20 nm 1 nm – 100 nm
Softmatter
Size and shape of objects
Hard material
can change are fixed
Single colloidal objects
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Polymers and nanotechnologyConformation and size of single macromolcules
End-to-end distance (Fadenendenabstand)
Radius of gyration (Trägheitsabstand)
Persistence length (Persistenzlänge)
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Polymers and nanotechnology
Self assembly
can change are fixed
Assemblies of nanoobjects
Ion channels
Functionallity
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Micro- and nanostructures through self-assembly
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Micro- and nanostructures through lithographic approaches
L. Jay Guo,*,† Xing Cheng,† and Chia-Fu Chou*,‡
NANO LETTERS 2004 Vol. 4, No. 1 69-73
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Micro- and nanotechnology as multidisciplinary fields
Molecular- / Cell- Biology
Chemistry
Engineering sciences
Physics
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Micro- and nanotechnology as multidisciplinary fields
Physics
Fundamentals for structuring technologies
Short wavelength radiation from synchrotons
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Micro- and nanotechnology as multidisciplinary fields
Physics
Single molecule physics
Moving single molecules
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Micro- and nanotechnology as multidisciplinary fields
Physics
Fundamentals for new analytical techniques
SXM (AFM) SXM (SNOM)
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Micro- and nanotechnology as multidisciplinary fields
Chemical tuning of surfaces
Control of Wettability
Chemistry
Spatial control of Reactivity
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Micro- and nanotechnology as multidisciplinary fields
Design of complex structures (for new high tech applications)
Chemistry
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Colloidal particles and their assemblyColloidosomes
A. D. Dinsmore, et al. Science 298, 1006 (2002)
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Micro- and nanotechnology as multidisciplinary fields
Nature as lecturer – Biomimetic approach
Chemistry
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Micro- and nanotechnology as multidisciplinary fields
Nature as lecturer – Molecular motors in biology (translation & rotation)
Molecular- / Cell- Biology
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Micro- and nanotechnology as multidisciplinary fields
Man-machine interfacingIntegrating biological function into microsystems
Engineering sciences
Neuron attached to a microchip(MPI Martinsried- Munich)
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2‘ nd lecture 09.11.2009
Lithographical MethodsPhysical Principles
TechnologiesMaterials
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Polymers in micro- and nanotechnology
3d structures2d structuresLateral structures
DNA Chip Microfluidic channel
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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,..)
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Ebeam and optical lithography
Substrate
Resist layer
Resist layerPositive resist
(becomes soluble upon irradiation)Negative resist
(becomes insoluble upon irradiation)
Pattern transfer
Irradiation
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Wetting of (polymer) solutions on solid substrates
ω ~ 0 deg. Spreading
0 < ω < 90 deg. Wetting
ω > 90 deg. Non-wetting
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Wetting and dewetting of thin polymer (liquid films) on solidsubstrates
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Stability of thin films on surfaces
R. Seemann, S. Herminghaus, and K. Jacobs, PRL 86 (2001) 5534
SiSiOPolymerfilm
dh
h: thickness of polymer filmd: Thickness of SiO layer
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Stability of thin films on surfaces on variable SiO interface
R. Seemann, S. Herminghaus, and K. Jacobs, PRL 86 (2001) 5534
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Optical lithography
Thick layer resist technology : High aspect ratios
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Optical lithography
Thick layer resist technology : High aspect ratios
H
I(d)
I(d) = I * exp- ε * d
Inhomogeneous irradiation of polymer due to strong optical absorption (H > 100 µm)
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Optical lithography
T-BOC cleavage
Acid catalyst negative resist
Alkaline development
Chemically amplified negative resist
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3‘ rd lecture 25.10.2010
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Optical lithography
Lenses for ArF laser sources (198 nm)
Structure resolution 80 nm
Increasing na to ~ 1.3
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Optical lithography
Resist for 157 nm VUV Lithography
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Optical lithography
Two-photon lithography for complex 3d structures
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Optical lithography
Two-photon lithography for complex 3d structures
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Optical lithographyin aqueous solutions
Jhaveri, et. al. Chem. Mater. 2009, 21 (10), 2004 ff.
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Optical lithography2 Photon photoabsorption
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Optical lithographyin aqueous solutions
Jhaveri, et. al. Chem. Mater. 2009, 21 (10), 2004 ff.
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Maskless optical lithography - A simple setup
Musgraves et. al. Am. J. Phys. 2005, 73 (10), 980 ff.
100 µm lines 500 µm pitch
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Maskless optical lithography – 3d stereolithography
Choi et. al. J. Mat. Process. Tech. 209, 2009, 5494 ff.
Kidney scaffold
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DMD chip element
Monk et. al. Microelectronic Eng., 27, 1995, 489 ff.
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Optical lithography in µ-fluidic systems – Particle assembly
Chung et. al. Nature Materials 7, 2008, 581 ff.
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Multi-LED array
Grossmann et. al. J. Neural Eng., 11, 2010, 016004 ff.
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Ebeam lithography Penetration depth of electrons with different energies
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Ebeam lithography Resolution down to 8 nm (A. Tilke LMU München) – Resist: Calixarene
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Ebeam lithography SCALPEL Technique
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Synchroton lithography / SynchrotonX-rays
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Synchroton lithography / Mask productionX-rays
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Polymer embossing
Embossing machine(Jenoptik)
Process stepsCycle time ~ 7 minutes
Heating of substrate and tools above Tg
Application of pressure (~ kN)
Cooling of substrate and embossingtool below Tg
Removal of tool
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Microdropdeposition
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Polydimethylsiloxane (PDMS) - The material
Chemical modification by hydrosilylation
(-O-CH2-CH2)- EO
Hydrophilic
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Polydimethylsiloxane (PDMS) - The material
Jessamine Ng Lee, Cheolmin Park,† and George M. Whitesides*
Anal. Chem.2003, 75,6544-6554
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Liquid filling of a capillary by Surface interactions
S. Stark,Microelectronic Eng. 67/68, 229 (2003)
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S. Stark,Microelectronic Eng. 67/68, 229 (2003)
Liquid filling of a capillary by Surface interactions
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Polydimethylsiloxane (PDMS) - The material
Compression mold 2 N/mm2
Compression mold 9.7 N/mm2
Schmid,H. Macromolecules 33, 3042 (2000)
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Permeation induced flow in PDMS channels
P. Silberzan, Europhys. Letters 68, 412 (2004)
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TIRF measurement of particle velocity near surfaces
K.Breuer2003 ASME International Mechanical Engineering Congress & ExpositionWashington, D.C., November 16-21, 2003
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TIRF measurement of particle velocity near surfaces
K.Breuer2003 ASME International Mechanical Engineering Congress & ExpositionWashington, D.C., November 16-21, 2003
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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
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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
UV induced radical polymerisation of polyurethaneacrylates
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Rigiflex lithography
Se-Jin Choi,† Pil J. Yoo,‡ Seung J. Baek,† Tae W. Kim,† and Hong H. Lee*,‡J. AM. CHEM. SOC. 2004, 126, 7744-7745
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Rigiflex lithography
Se-Jin Choi,† Pil J. Yoo,‡ Seung J. Baek,† Tae W. Kim,† and Hong H. Lee*,‡J. AM. CHEM. SOC. 2004, 126, 7744-7745
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PDMS based complex microfluidic systems
S. Quake,Science 298, 580 (2002)
Multilayer µ-fluidic systems
a) Fluidic transport layer
b) Control layer
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Complex shaped 3d nanoparticles
S.E.A. Gratton et al. / Journal of Controlled Release 121 (2007) 10–18
Larken E. Euliss, Julie A. DuPont, Stephanie Gratton and Joseph DeSimoneChem. Soc. Rev., 2006, 35, 1095–1104
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Complex shaped 3d nanoparticles
Jason P. Rolland,† Benjamin W. Maynor,† Larken E. Euliss,† Ansley E. Exner,†Ginger M. Denison,† and Joseph M. DeSimoneJ. AM. CHEM. SOC. 9 VOL. 127, NO. 28, 2005 10099
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Complex shaped 3d nanoparticles
Larken E. Euliss, Julie A. DuPont, Stephanie Gratton and Joseph DeSimoneChem. Soc. Rev., 2006, 35, 1095–1104