title: A photolithographic approach to spatially resolved cross-linked nanolayers.
abstract: The preparation of cross-linked nanosheets with 1-2 nm thickness and predefined shape was achieved by lithographic immobilization of trimethacryloyl thioalkanoates onto the surface of Si wafers, which were functionalized with 2-(phenacylthio)acetamido groups via a photoinduced reaction. Subsequent cross-linking via free radical polymerization as well as a phototriggered Diels-Alder reaction under mild conditions on the surface led to the desired nanosheets. Electrospray ionization mass spectrometry (ESI-MS), X-ray photoelectron spectroscopy (XPS), time-of-flight secondary ion mass spectrometry (ToF-SIMS), as well as infrared reflection-absorption spectroscopy (IRRAS) confirmed the success of individual surface-modification and cross-linking reactions. The thickness and lateral size of the cross-linked structures were determined by atomic force microscopy (AFM) for samples prepared on Si wafers functionalized with a self-assembled monolayer of 1H,1H,2H,2H-perfluorodecyl groups bearing circular pores obtained via a polymer blend lithographic approach, which led to the cross-linking reactions occurring in circular nanoareas (diameter of 50-640 nm) yielding an average thickness of 1.2 nm (radical cross-linking), 1.8 nm (radical cross-linking in the presence of 2,2,2-trifluoroethyl methacrylate as a comonomer), and 1.1 nm (photochemical cross-linking) of the nanosheets.
authors.affiliation: †Preparative Macromolecular Chemistry, Institut für Technische Chemie und Polymerchemie (ITPC), Karlsruhe Institute of Technology (KIT), Engesserstr. 18, 76128 Karlsruhe, Germany.|‡Laboratory of Applied Chemistry, Institute of Organic Chemistry (IOC), Karlsruhe Institute of Technology (KIT), Fritz-Haber-Weg 6, 76131 Karlsruhe, Germany.
authors.forename: Keita
authors.initials: K
authors.lastname: Fuchise
authors.affiliation: §Institute of Functional Interfaces (IFG), Karlsruhe Institute of Technology (KIT), Hermann-von-Helmholtz-Platz 1, 76344 Eggenstein-Leopoldshafen, Germany.
authors.forename: Peter
authors.initials: P
authors.lastname: Lindemann
authors.affiliation: §Institute of Functional Interfaces (IFG), Karlsruhe Institute of Technology (KIT), Hermann-von-Helmholtz-Platz 1, 76344 Eggenstein-Leopoldshafen, Germany.
authors.forename: Stefan
authors.initials: S
authors.lastname: Heißler
authors.affiliation: §Institute of Functional Interfaces (IFG), Karlsruhe Institute of Technology (KIT), Hermann-von-Helmholtz-Platz 1, 76344 Eggenstein-Leopoldshafen, Germany.
authors.forename: Hartmut
authors.initials: H
authors.lastname: Gliemann
authors.affiliation: ∥Institut für Angewandte Materialien (IAM) and Karlsruhe Nano Micro Facility (KNMF), Karlsruhe Institute of Technology (KIT), Hermann-von-Helmholtz-Platz 1, 76344 Eggenstein-Leopoldshafen, Germany.
authors.forename: Vanessa
authors.initials: V
authors.lastname: Trouillet
authors.affiliation: †Preparative Macromolecular Chemistry, Institut für Technische Chemie und Polymerchemie (ITPC), Karlsruhe Institute of Technology (KIT), Engesserstr. 18, 76128 Karlsruhe, Germany.|⊥Institut für Biologische Grenzflächen (IBG), Karlsruhe Institute of Technology (KIT), Hermann-von-Helmholtz-Platz 1, 76344 Eggenstein-Leopoldshafen, Germany.
authors.forename: Alexander
authors.initials: A
authors.lastname: Welle
authors.affiliation: #Institute of Nanotechnology (INT), Karlsruhe Institute of Technology (KIT), Hermann-von-Helmholtz-Platz 1, 76344 Eggenstein-Leopoldshafen, Germany.|∇Institute of Applied Physics and Center for Functional Nanostructures (CFN), Karlsruhe Institute of Technology (KIT), 76128 Karlsruhe, Germany.
authors.forename: Jonathan
authors.initials: J
authors.lastname: Berson
authors.affiliation: #Institute of Nanotechnology (INT), Karlsruhe Institute of Technology (KIT), Hermann-von-Helmholtz-Platz 1, 76344 Eggenstein-Leopoldshafen, Germany.|∇Institute of Applied Physics and Center for Functional Nanostructures (CFN), Karlsruhe Institute of Technology (KIT), 76128 Karlsruhe, Germany.
authors.forename: Stefan
authors.initials: S
authors.lastname: Walheim
authors.affiliation: #Institute of Nanotechnology (INT), Karlsruhe Institute of Technology (KIT), Hermann-von-Helmholtz-Platz 1, 76344 Eggenstein-Leopoldshafen, Germany.|∇Institute of Applied Physics and Center for Functional Nanostructures (CFN), Karlsruhe Institute of Technology (KIT), 76128 Karlsruhe, Germany.
authors.forename: Thomas
authors.initials: T
authors.lastname: Schimmel
authors.affiliation: ‡Laboratory of Applied Chemistry, Institute of Organic Chemistry (IOC), Karlsruhe Institute of Technology (KIT), Fritz-Haber-Weg 6, 76131 Karlsruhe, Germany.
authors.forename: Michael A R
authors.initials: MA
authors.lastname: Meier
authors.affiliation: †Preparative Macromolecular Chemistry, Institut für Technische Chemie und Polymerchemie (ITPC), Karlsruhe Institute of Technology (KIT), Engesserstr. 18, 76128 Karlsruhe, Germany.|⊥Institut für Biologische Grenzflächen (IBG), Karlsruhe Institute of Technology (KIT), Hermann-von-Helmholtz-Platz 1, 76344 Eggenstein-Leopoldshafen, Germany.
authors.forename: Christopher
authors.initials: C
authors.lastname: Barner-Kowollik
mesh_terms: D000081:Acetamides / Q000737:chemistry; D002264:Carboxylic Acids / Q000737:chemistry; D049329:Nanostructures / Q000737:chemistry*; D036103:Nanotechnology / Q000379:methods*; D055668:Photochemical Processes; D012825:Silicon / Q000737:chemistry*; D013499:Surface Properties
chemical_list: D000081:Acetamides; D002264:Carboxylic Acids; C030686:acetamide; D012825:Silicon