Stimulated Emission Depletion Lithography with Mercapto-Functional Polymers

Surface reactive nanostructures were fabricated using stimulated emission depletion (STED) lithography. The functionalization of the nanostructures was realized by copolymerization of a bifunctional metal oxo cluster in the presence of a triacrylate monomer. Ligands of the cluster surface cross-link to the monomer during the lithographic process, whereas unreacted mercapto functionalized ligands are transferred to the polymer and remain reactive after polymer formation of the surface of the nanostructure. The depletion efficiency in dependence of the cluster loading was investigated and full depletion of the STED effect was observed with a cluster loading exceeding 4 wt %. A feature size by λ/11 was achieved by using a donut-shaped depletion beam. The reactivity of the mercapto groups on the surface of the nanostructure was tested by incubation with mercapto-reactive fluorophores.

[1]  Karlheinz Schwarz,et al.  Ligand dynamics on the surface of zirconium oxo clusters. , 2009, Physical chemistry chemical physics : PCCP.

[2]  Costas Fotakis,et al.  3D conducting nanostructures fabricated using direct laser writing , 2011 .

[3]  R. Lévy,et al.  Measuring the spring constant of atomic force microscope cantilevers: thermal fluctuations and other methods , 2002 .

[4]  T. Klar,et al.  Streptavidin functionalized polymer nanodots fabricated by visible light lithography , 2015, Journal of Nanobiotechnology.

[5]  T. Klar,et al.  Nano-anchors with single protein capacity produced with STED lithography. , 2013, Nano letters.

[6]  U. Schubert.  Organofunctional Metal Oxide Clusters as Building Blocks for Inorganic—Organic Hybrid Materials , 2005 .

[7]  Martin Wegener,et al.  Exploring the Mechanisms in STED‐Enhanced Direct Laser Writing , 2015 .

[8]  U. Schubert.  Inorganic‐Organic Hybrid Polymers Based on Surface‐Modified Metal Oxide Clusters , 2008 .

[9]  Benjamin Richter,et al.  Preparation of reactive three-dimensional microstructures via direct laser writing and thiol-ene chemistry. , 2013, Macromolecular rapid communications.

[10]  R. Stark,et al.  Thermomechanical noise of a free v-shaped cantilever for atomic-force microscopy. , 2001, Ultramicroscopy.

[11]  U. Schubert.  Polymers Reinforced by Covalently Bonded Inorganic Clusters , 2001 .

[12]  Robert R McLeod,et al.  Two-Color Single-Photon Photoinitiation and Photoinhibition for Subdiffraction Photolithography , 2009, Science.

[13]  S. Hell,et al.  Fluorescence microscopy with diffraction resolution barrier broken by stimulated emission. , 2000, Proceedings of the National Academy of Sciences of the United States of America.

[14]  A. Priola,et al.  Thiol-ene Hybrid Organic/Inorganic Nanostructured Coatings Based on Thiol-Functionalized Zirconium Oxoclusters , 2007 .

[15]  S. Hell,et al.  Subdiffraction resolution in far-field fluorescence microscopy. , 1999, Optics letters.

[16]  J. Bechhoefer,et al.  Calibration of atomic‐force microscope tips , 1993 .

[17]  Martin Wegener,et al.  Polymerization Kinetics in Three‐Dimensional Direct Laser Writing , 2014, Advanced materials.

[18]  Valentin Satzinger,et al.  Two-photon-induced thiol-ene polymerization as a fabrication tool for flexible optical waveguides , 2014 .

[19]  Mangirdas Malinauskas,et al.  In vitro and in vivo biocompatibility study on laser 3D microstructurable polymers , 2012 .

[20]  Aleksandr Ovsianikov,et al.  Engineering 3D cell-culture matrices: multiphoton processing technologies for biological and tissue engineering applications , 2012, Expert review of medical devices.

[21]  Jaroslaw Jacak,et al.  120 nm resolution and 55 nm structure size in STED-lithography. , 2013, Optics express.

[22]  Christian Eggeling,et al.  STED microscopy reveals crystal colour centres with nanometric resolution. , 2009 .

[23]  M. Wegener,et al.  Subcellular stretch-induced cytoskeletal response of single fibroblasts within 3D designer scaffolds. , 2015, Biomaterials.

[24]  Aleksandr Ovsianikov,et al.  Engineering 3 D cell-culture matrices : multiphoton processing technologies for biological and tissue engineering applications , 2013 .

[25]  J. Fischer,et al.  Three‐dimensional optical laser lithography beyond the diffraction limit , 2013 .

[26]  J. Fischer,et al.  Pump-probe spectroscopy on photoinitiators for stimulated-emission-depletion optical lithography. , 2011, Optics letters.

[27]  Maria Farsari,et al.  Three‐Dimensional Metallic Photonic Crystals with Optical Bandgaps , 2012, Advanced materials.

[28]  Georg von Freymann,et al.  The Materials Challenge in Diffraction‐Unlimited Direct‐Laser‐Writing Optical Lithography , 2010, Advanced materials.

[29]  A. Stiegman,et al.  High Refractive Index Polymer Composites Synthesized by Cross‐Linking of Oxozirconium Clusters Through Thiol‐Ene Polymerization , 2015 .

[30]  U. Schubert,et al.  Retention of the Cluster Core Structure during Ligand Exchange Reactions of Carboxylato-Substituted Metal Oxo Clusters , 2015, European journal of inorganic chemistry.

[31]  Yon-Kyu Park,et al.  Accurate determination of spring constant of atomic force microscope cantilevers and comparison with other methods , 2010 .

[32]  A. Diaspro,et al.  Photopolymerization Inhibition Dynamics for Sub-Diffraction Direct Laser Writing Lithography , 2012, Chemphyschem : a European journal of chemical physics and physical chemistry.

[33]  Yaoyu Cao,et al.  Three-dimensional deep sub-diffraction optical beam lithography with 9 nm feature size , 2013, Nature Communications.

[34]  Ali Khademhosseini,et al.  Microscale Strategies for Generating Cell-Encapsulating Hydrogels. , 2012, Polymers.

[35]  Martin Wegener,et al.  Direct laser writing of three-dimensional submicron structures using a continuous-wave laser at 532 nm , 2010 .

[36]  Martin Wegener,et al.  Three-dimensional micro-printing of temperature sensors based on up-conversion luminescence , 2015 .

[37]  S. Hell,et al.  Breaking the diffraction resolution limit by stimulated emission: stimulated-emission-depletion fluorescence microscopy. , 1994, Optics letters.

[38]  Min Gu,et al.  Optical storage arrays: a perspective for future big data storage , 2014, Light: Science & Applications.

[39]  Shoji Maruo,et al.  Three-dimensional microfabrication with two-photon absorbed photopolymerization , 1996, International Commission for Optics.

[40]  M. Wegener,et al.  Two‐Component Polymer Scaffolds for Controlled Three‐Dimensional Cell Culture , 2011, Advanced materials.

[41]  R. Gattass,et al.  Achieving λ/20 Resolution by One-Color Initiation and Deactivation of Polymerization , 2009, Science.

[42]  R. Maggio,et al.  High temperature resistant silane/zirconium-oxocluster hybrid copolymers containing “free” thiol/ene functionalities in the polymer matrix , 2013 .

[43]  Ulrich S. Schubert,et al.  Oxozirconium Methacrylate Clusters: Zr6(OH)4O4(OMc)12 and Zr4O2(OMc)12 (OMc = Methacrylate) , 1997 .