Morphology Evolution in Slowly Dip-Coated Supramolecular PS-b-P4VP Thin Films

Block copolymer films obtained by dip-coating have been much less studied than those obtained by spin-coating, although it is an important industrial process. In our investigations of supramolecular diblock copolymer films of PS–P4VP (∼30 wt % P4VP) dip-coated from THF solutions, we initially found that films containing a monohydroxy-functionalized small molecule (SM), 1-naphthol (NOH), have a dot morphology, whereas those containing a monocarboxylic acid-functionalized small molecule, 1-naphthoic acid (NCOOH), have a stripe morphology. The COOH functionality is known to hydrogen bond more strongly to pyridine than OH. Yet the total amount of SM in the two types of films under given conditions is the same and PS–P4VP/NOH and PS–P4VP/NCOOH (equimolar SM:VP) in THF solution are both micellar, with the same spherical shape and size as PS–P4VP alone. On the other hand, the stripe morphology can be transformed to dot morphology by decreasing the dip-coating rate, the solution concentration or the SM:VP molar r...

[1]  C. Bazuin,et al.  A Study of the Supramolecular Approach in Controlling Diblock Copolymer Nanopatterning and Nanoporosity on Surfaces , 2006 .

[2]  X. Li,et al.  Facile Synthesis of Nanostructured Carbon through Self‐Assembly between Block Copolymers and Carbohydrates , 2007 .

[3]  Soojin Park,et al.  A simple route to highly oriented and ordered nanoporous block copolymer templates. , 2008, ACS nano.

[4]  Marco Faustini,et al.  Preparation of Sol−Gel Films by Dip-Coating in Extreme Conditions , 2010 .

[5]  Nicola J. Ferrier,et al.  Dimensional Scaling of Cylinders in Thin Films of Block Copolymer-Homopolymer Ternary Blends , 2009 .

[6]  T. Hashimoto,et al.  Order−Order Phase Transition between Spherical and Cylindrical Microdomain Structures of Block Copolymer. I. Mechanism of the Transition , 2000 .

[7]  Kunlun Hong,et al.  Synthesis of a large-scale highly ordered porous carbon film by self-assembly of block copolymers. , 2004, Angewandte Chemie.

[8]  Markus Antonietti,et al.  Determination of the micelle architecture of polystyrene poly(4-vinylpyridine) block copolymers in dilute solution , 1994 .

[9]  S. Tung,et al.  Hierarchical Assemblies of Block-Copolymer-Based Supramolecules in Thin Films , 2008 .

[10]  G. Brinke,et al.  Thin films of complexed block copolymers , 2009 .

[11]  R. Register,et al.  Controlling order in block copolymer thin films for nanopatterning applications. , 2010, Annual review of chemical and biomolecular engineering.

[12]  Yanchun Han,et al.  Surface morphology evolution of poly(styrene-block-4-vinylpyridine) (PS-b-P4VP)(H+) and poly(methyl methacrylate)-dibenzo-18-crown-6-poly(methyl methacrylate) (PMCMA) supramolecular film , 2007 .

[13]  Kookheon Char,et al.  Surfactant‐Assisted Orientation of Thin Diblock Copolymer Films , 2008 .

[14]  Bhanu Nandan,et al.  Composition-Dependent Morphological Transitions and Pathways in Switching of Fine Structure in Thin Films of Block Copolymer Supramolecular Assemblies , 2010 .

[15]  Wei-Han Huang,et al.  Effects of Annealing Solvents on the Morphology of Block Copolymer-Based Supramolecular Thin Films , 2012 .

[16]  S. Tung,et al.  Microdomain control in block copolymer-based supramolecular thin films through varying the grafting density of additives , 2011 .

[17]  A. Sidorenko,et al.  Block Copolymer Supramolecular Assembly beyond Hydrogen Bonding , 2012 .

[18]  M. J. Robbins,et al.  Modelling approaches to the dewetting of evaporating thin films of nanoparticle suspensions , 2009, Journal of physics. Condensed matter : an Institute of Physics journal.

[19]  T. Dupont,et al.  Capillary flow as the cause of ring stains from dried liquid drops , 1997, Nature.

[20]  S. Minko,et al.  Microphase Separation in Thin Films of Poly(styrene-block-4-vinylpyridine) Copolymer−2-(4‘-Hydroxybenzeneazo)benzoic Acid Assembly , 2005 .

[21]  A. Mayes,et al.  Block copolymer thin films : Physics and applications , 2001 .

[22]  J. Isasi,et al.  Hydrogen bonding in poly(4-vinylpyridine)/poly(vinyl acetate-co-vinyl alcohol) blends. An infrared study , 1993 .

[23]  A. Karim,et al.  Ordering in asymmetric poly (ethylene–propylene)–poly (ethylethylene) diblock copolymer thin films , 1994 .

[24]  B. Kuila,et al.  Block copolymer–small molecule supramolecular assembly in thin film: a novel tool for surface patterning of different functional nanomaterials , 2011 .

[25]  T. P. Russell,et al.  Solvent‐Induced Ordering in Thin Film Diblock Copolymer/Homopolymer Mixtures , 2004 .

[26]  O. Ikkala,et al.  Phase behavior of solvent vapor annealed thin films of PS-b-P4VP(PDP) supramolecules , 2008 .

[27]  Makinen,et al.  Switching supramolecular polymeric materials with multiple length scales , 1998, Science.

[28]  K. Stebe,et al.  Spontaneous pattern formation by dip coating of colloidal suspensions on homogeneous surfaces. , 2007, Langmuir : the ACS journal of surfaces and colloids.

[29]  S. Tolbert,et al.  Controlling thickness in hexagonal polymer templated mesoporous silica films , 2006 .

[30]  G. Sauer,et al.  Microdomain Morphology of Thin ABC Triblock Copolymer Films , 1999 .

[31]  A. Knoll,et al.  Nanoscaling of microdomain spacings in thin films of cylinder-forming block copolymers. , 2007, Nano letters.

[32]  G. Brinke,et al.  Hierarchical Terrace Formation in PS-b-P4VP(PDP) Supramolecular Thin Films , 2008 .

[33]  W. Bras,et al.  Self-Assembly of Supramolecules Consisting of Octyl Gallate Hydrogen Bonded to Polyisoprene-block-poly(vinylpyridine) Diblock Copolymers , 2004 .

[34]  E. B. Gowd,et al.  Supramolecular Assembly of Poly(styrene)-b-poly(4-vinylpyridine) and 1-Pyrenebutyric Acid in Thin Film and Their Use for Nanofabrication , 2010 .

[35]  Bhanu Nandan,et al.  Thin films of block copolymer supramolecular assemblies: Microphase separation and nanofabrication , 2010 .

[36]  M. Hillmyer,et al.  Templating Nanoporous Polymers with Ordered Block Copolymers , 2008 .

[37]  P. Formánek,et al.  Moiré Patterns in Superimposed Nanoporous Thin Films Derived from Block-Copolymer Assemblies , 2007 .

[38]  Jens-Christian Meiners,et al.  Chemically functionalized surfaces from ultrathin block-copolymer films , 1996 .

[39]  Jillian M. Buriak,et al.  Assembly of aligned linear metallic patterns on silicon , 2007, Nature Nanotechnology.

[40]  S. Minko,et al.  Metallic nickel nanorod arrays embedded into ordered block copolymer templates , 2007 .

[41]  Ian W. Hamley,et al.  Ordering in thin films of block copolymers: Fundamentals to potential applications , 2009 .

[42]  Gallagher,et al.  Observed frustration in confined block copolymers. , 1994, Physical review letters.

[43]  I. Hamley,et al.  Nanotechnology with soft materials. , 2003, Angewandte Chemie.

[44]  S. Darling.  Directing the self-assembly of block copolymers , 2007 .

[45]  A. Fujishima,et al.  Molecular self-assembly of liquid crystalline side-chain polymers through intermolecular hydrogen bonding. Polymeric complexes built from a polyacrylate and stilbazoles , 1992 .

[46]  J. Buriak,et al.  Block copolymer templated etching on silicon. , 2007, Nano letters.

[47]  Christopher K. Ober,et al.  Patternable block copolymers , 2005 .

[48]  Todd Emrick,et al.  Self-directed self-assembly of nanoparticle/copolymer mixtures , 2005, Nature.

[49]  Yongzhong Chen,et al.  Effect of the Nature of Annealing Solvent on the Morphology of Diblock Copolymer Blend Thin Films , 2008 .

[50]  J. Meiners,et al.  Adsorption of block-copolymer micelles from a selective solvent , 1997 .

[51]  S. Satija,et al.  Homopolymer distributions in ordered block copolymers , 1992 .

[52]  Sergiy Minko,et al.  Ordered reactive nanomembranes/nanotemplates from thin films of block copolymer supramolecular assembly. , 2003, Journal of the American Chemical Society.

[53]  Jin Kon Kim,et al.  Precise Control of Nanopore Size in Thin Film Using Mixtures of Asymmetric Block Copolymer and Homopolymer , 2003 .

[54]  J. Meiners,et al.  Two-dimensional micelle formation of polystyrene-poly(vinylpyridine) diblock copolymers on mice surfaces , 1995 .

[55]  M. Rafailovich,et al.  SELF-ORDERING OF DIBLOCK COPOLYMERS FROM SOLUTION , 1996 .

[56]  K. Loos,et al.  Nanostructured polystyrene-block-poly(4-vinyl pyridine)(pentadecylphenol) thin films as templates for polypyrrole synthesis , 2009 .

[57]  M. Antonietti,et al.  Microgels: model polymers for the crosslinked state , 1990 .

[58]  Robert M. Briber,et al.  A simple method for creating nanoporous block-copolymer thin films , 2010 .

[59]  E. Thomas,et al.  Supramolecular Routes to Hierarchical Structures: Comb-Coil Diblock Copolymers Organized with Two Length Scales , 1999 .

[60]  Dong Ha Kim,et al.  Volume Contractions Induced by Crosslinking: A Novel Route to Nanoporous Polymer Films , 2003 .

[61]  Yanchun Han,et al.  Surface morphology evolution of a thin polymeric supramolecular film by tuning interactions , 2006 .

[62]  O. Ikkala,et al.  Supramolecular polymeric materials with hierarchical structure-within-structure morphologies , 1999 .

[63]  David Grosso,et al.  How to exploit the full potential of the dip-coating process to better control film formation , 2011 .

[64]  Malcolm R. Mackley,et al.  Spin and dip coating of light-emitting polymer solutions: Matching experiment with modelling , 2006 .

[65]  A. Stannard.  Dewetting-mediated pattern formation in nanoparticle assemblies , 2011, Journal of physics. Condensed matter : an Institute of Physics journal.

[66]  E. Pauliac-Vaujour,et al.  Fingering instabilities in dewetting nanofluids. , 2008, Physical review letters.

[67]  C. Bazuin,et al.  Mixtures of an Acid-Functionalized Mesogen with Poly(4-vinylpyridine) , 1996 .

[68]  Edward L Cussler,et al.  Cylinder Orientation Mechanism in Block Copolymer Thin Films Upon Solvent Evaporation , 2010 .