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Tutorial on Plasma Polymerization Deposition of Functionalized Films

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Tutorial on Plasma Polymerization Deposition of Functionalized Films Tutorial on Plasma Polymerization Deposition of Functionalized Films A. Michelmore, D.A. Steele, J.D. Whittle, J.W. Bradley, R.D. Short University of South Australia Based upon review article RSC Advances, 2013, 3, 13540-13557 Mawson Institute Tutorial covers • Introduction – Technological importance of plasma polymers + examples • The plasma phase – Plasma – surface interactions – Mechanisms of deposition - examines W/F - early stages of film grow - the role of ions Introduction to Plasma polymerization • Plasma ignited in organic vapour – Pure vapour or a mixture of vapours – Reduced pressure • Polymer (organic) deposit formed on all surfaces • Chemistry of deposit often similar to vapour (monomer) – Polymerisation not dependent on functional group – Plasma polymers tailored from organic to “inorganic” General properties of plasma polymers • Ultra-thin (< 50nm) • Soluble/Insoluble • Trapped free radicals • Adherent • Conformal • Pinhole free • Internal stress – Will crack and flake if too thick Mawson Institute Plasma polymerization is the ultimate enabling technology Hydrophobic/Hydrophobic Functionalized films Chemical Gradients Responsive “intelligent” surfaces Mawson Institute Example - Super hydrophobic coatings • Produced by pulsed plasma polymerization - Highly fluorinated monomers, e.g. TFE • Large amount of conventional PTFE in ‘ribbons’ - Rough surface • In continuous wave mode no ‘ribbons’ on surface - Ribbons grow in ‘off’ period from activated sites Mawson Institute Example - Treatment of Burns • In myskinTM technology a plasma polymerized coating is applied to a bandage to allow the culture of patient’s own cells • Cells are delivered “off” pp-coated bandage - Highly effective way of getting cells to patients rapidly - Used in treatment of severe burns • Range of potential applications Haddow et al., Plasma Processes Polym., 2006, 3, 419 Renaissance in plasma polymerization: • Traditionally, <1990s, scratch resistance, barrier layer, wetting – E.g. Nature, 1966, 209, 769 • Recent-cited applications: - Coating of tissue engineering scaffolds (Adv. Mater., 2006, 18,1406) - Functionalization of nanotubes for covalent coupling of quantum dots (Adv. Mater., 2007, 19, 4003) - Fabrication of a microcantilever fast humidity sensor (Adv. Mater., 2007, 19, 4248) - Micro- and nano-engineering of surface structures (Adv. Mater., 2006, 18, 1406; Adv. Mater., 2007, 19, 1947; Adv. Mater., 2010, 22, , 1451) - Surfaces for high-throughput screening devices (Adv. Mater., 2008, 20, 116; Lab on a Chip, 2011, 11, 541) Mawson Institute Making a plasma polymer What do you need to start? Mawson Institute Reactor • Enclosed chamber - Means to introduce monomer as vapour - Reduced pressure ~1Pa – 100Pa - (~0.75 mTorr- 75mTorr) • Method of excitation DC or AC (RF→MW), CW or pulsed Mawson Institute RF excitation preferred for plasma polymers • Electric fields heat electrons, generate plasma –See Tutorial 2 – The Plasma Phase • Advantages of RF –Displacement rather than particle currents –Stability –Higher electrons temperature –Process insulating materials without sputtering at electrodes Mawson Institute Plasma polymerization: Plasma Chamber (under vacuum) Gas (Monomer Vapour) Flows into Chamber Radiofrequency Power Applied to System Substrate Plasma Mawson Institute Reactor design – Historical Perspective (a) Clark and Dilks reactor design 1977 [ref 18] and three decades of reactor design evolution since, illustrating a variety of electrode configurations, power supplies and diagnostic tools (b) Ward 1989 [19] (c) Lopez et al. 1992 [20] (d) O’Toole et al. 1995 [21] (e) Favia et al., 1996 [22] (f) Candan et al. 1998 [23] (g) Alexander et al. 1998 [24] (h) Voronin et al. 2006 [25] A. Michelmore et al, RSC Advances, 2013, 3, 13540 Mawson Institute Plasma polymerization Ions Photons Fragments Electrons Gas Intact Monomer (Monomer) Atoms Plasma phase Radicals interactions:- Oligomers Excitation, Ionisation, Metastables Relaxation, Ion-Molecule, Radical-Neutral, Fragmentation Energy transfer Desorption Chemical modification Etching (Deposition Adsorption Grafting) Substrate Mawson Institute Plasma parameters: RF Power, Gas Flowrate, Pressure, Ion Density Electron Temperature, Bias Potentials etc Different types of coating Non-functionalized Functionalized Mawson Institute .
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