Printed Thin Diblock Copolymer Films with Dense Magnetic Nanostructure.

Thin hybrid films with dense magnetic structures for sensor applications are printed using diblock copolymer (DBC) templating magnetic nanoparticles (MNPs). To achieve a high-density magnetic structure, the printing ink is prepared by mixing polystyrene- block-poly(methyl methacrylate) (PS- b-PMMA) with a large PS volume fraction and PS selective MNPs. Solvent vapor annealing is applied to generate a parallel cylindrical film morphology (with respect to the substrate), in which the MNP-residing PS domains are well separated by the PMMA matrix, and thus, the formation of large MNP agglomerates is avoided. Moreover, the morphologies of the printed thin films are determined as a function of the MNP concentration with real and reciprocal space characterization techniques. The PS domains are found to be saturated with MNPs at 1 wt %, at which the structural order of the hybrid films reaches a maximum within the studied range of MNP concentration. As a beneficial aspect, the MNP loading improves the morphological order of the thin DBC films. The dense magnetic structure endows the thin films with a faster superparamagnetic responsive behavior, as compared to thick films where identical MNPs are used, but dispersed inside the minority domains of the DBC.

[1]  V. Deline,et al.  Surface-induced orientation of symmetric, diblock copolymers: a secondary ion mass spectrometry study , 1989 .

[2]  Thomas P. Russell,et al.  Temperature dependence of the interaction parameter of polystyrene and poly(methyl methacrylate) , 1990 .

[3]  A. Mayes,et al.  A Free Energy Model for Confined Diblock Copolymers , 1994 .

[4]  A. Alivisatos.  Semiconductor Clusters, Nanocrystals, and Quantum Dots , 1996, Science.

[5]  G. Schmid,et al.  Quantum-size effects in the thermodynamic properties of metallic nanoparticles , 1996, Nature.

[6]  M. Stamm,et al.  Correlated roughness, long-range correlations, and dewetting of thin polymer films , 1998 .

[7]  Galen T. Pickett,et al.  Morphology of Ultrathin Supported Diblock Copolymer Films: Theory and Experiment , 2000 .

[8]  F. Dawson,et al.  Magnetic Nanocomposites: Preparation and Characterization of Polymer-Coated Iron Nanoparticles , 2002 .

[9]  P. Müller‐Buschbaum.  Grazing incidence small-angle X-ray scattering: an advanced scattering technique for the investigation of nanostructured polymer films , 2003, Analytical and bioanalytical chemistry.

[10]  P. Müller‐Buschbaum.  Dewetting and pattern formation in thin polymer films as investigated in real and reciprocal space , 2003 .

[11]  Dirk W. Schubert,et al.  Spin coating from a molecular point of view: its concentration regimes, influence of molar mass and distribution , 2003 .

[12]  D. Astruc,et al.  Gold nanoparticles: assembly, supramolecular chemistry, quantum-size-related properties, and applications toward biology, catalysis, and nanotechnology. , 2004, Chemical reviews.

[13]  Jin Kon Kim,et al.  Enhancement in the Orientation of the Microdomain in Block Copolymer Thin Films upon the Addition of Homopolymer , 2004 .

[14]  Yu Xuan,et al.  Solvent vapor induced dewetting in diblock copolymer thin films , 2005 .

[15]  S. Darling,et al.  Self‐Organization of FePt Nanoparticles on Photochemically Modified Diblock Copolymer Templates , 2005 .

[16]  S. Darling,et al.  A materials chemistry perspective on nanomagnetism , 2005 .

[17]  Moon Jeong Park,et al.  Effect of interacting nanoparticles on the ordered morphology of block copolymer/nanoparticle mixtures , 2006 .

[18]  Anna C. Balazs,et al.  Nanoparticle Polymer Composites: Where Two Small Worlds Meet , 2006, Science.

[19]  Yu Xuan,et al.  Morphologies in solvent-annealed thin films of symmetric diblock copolymer. , 2006, The Journal of chemical physics.

[20]  Hariharan Srikanth,et al.  Superparamagnetic Polymer Nanocomposites with Uniform Fe3O4 Nanoparticle Dispersions , 2006 .

[21]  Moon Jeong Park,et al.  Effect of the casting solvent on the morphology of poly(styrene-b-isoprene) diblock copolymer/magnetic nanoparticle mixtures. , 2006, Langmuir : the ACS journal of surfaces and colloids.

[22]  M. A. Kashem,et al.  Correlated Roughness in Polymer Films Containing Maghemite Nanoparticles , 2008 .

[23]  R. Composto,et al.  Dispersion of polymer-grafted magnetic nanoparticles in homopolymers and block copolymers , 2008 .

[24]  M. A. Kashem,et al.  Array of Magnetic Nanoparticles via Particle Co-operated Self-Assembly in Block Copolymer Thin Film , 2009 .

[25]  P. Müller‐Buschbaum,et al.  Polymer-template-assisted growth of gold nanowires using a novel flow-stream technique. , 2009, Langmuir : the ACS journal of surfaces and colloids.

[26]  Caroline A. Ross,et al.  Solvent‐Vapor‐Induced Tunability of Self‐Assembled Block Copolymer Patterns , 2009 .

[27]  M. Burghammer,et al.  Colloidal silver nanoparticle gradient layer prepared by drying between two walls of different wettability , 2009, Journal of physics. Condensed matter : an Institute of Physics journal.

[28]  Vikram K. Daga,et al.  Nanoparticle-driven assembly of block copolymers: a simple route to ordered hybrid materials. , 2011, Journal of the American Chemical Society.

[29]  I. Mondragon,et al.  Controlled placement of polystyrene-grafted CdSe nanoparticles in self-assembled block copolymers , 2013, Colloid and Polymer Science.

[30]  A. Alivisatos,et al.  Size-dependent assemblies of nanoparticle mixtures in thin films. , 2013, Journal of the American Chemical Society.

[31]  M. Morris,et al.  Solvent Vapor Annealing of Block Polymer Thin Films , 2013 .

[32]  Xinglu Huang,et al.  Self-assembly of amphiphilic plasmonic micelle-like nanoparticles in selective solvents. , 2013, Journal of the American Chemical Society.

[33]  Yuan Yao,et al.  Self-assembly of diblock copolymer-maghemite nanoparticle hybrid thin films. , 2014, ACS applied materials & interfaces.

[34]  Yuan Yao,et al.  Nano- and microstructures of magnetic field-guided maghemite nanoparticles in diblock copolymer films. , 2014, ACS applied materials & interfaces.

[35]  A. Eceiza,et al.  Generation of nanocomposites based on (PMMA-b-PCL)-grafted Fe2O3 nanoparticles and PS-b-PCL block copolymer , 2014 .

[36]  Yuan Yao,et al.  Arrangement of Maghemite Nanoparticles via Wet Chemical Self-Assembly in PS-b-PNIPAM Diblock Copolymer Films. , 2015, ACS applied materials & interfaces.

[37]  Yuan Yao,et al.  Patterned Diblock Co-Polymer Thin Films as Templates for Advanced Anisotropic Metal Nanostructures. , 2015, ACS applied materials & interfaces.

[38]  G. Kortaberria,et al.  Selective placement of magnetic Fe3O4 nanoparticles into the lamellar nanostructure of PS-b-PMMA diblock copolymer , 2015 .

[39]  Biswajit Sarkar,et al.  Block copolymer-nanoparticle composites: Structure, functional properties, and processing , 2015 .

[40]  Maurizio Fermeglia,et al.  Combined Mesoscale/Experimental Study of Selective Placement of Magnetic Nanoparticles in Diblock Copolymer Films via Solvent Vapor Annealing , 2016 .

[41]  Peng Huang,et al.  Magneto-Plasmonic Janus Vesicles for Magnetic Field-Enhanced Photoacoustic and Magnetic Resonance Imaging of Tumors. , 2016, Angewandte Chemie.

[42]  Yuan Yao,et al.  Lamellar Diblock Copolymer Films with Embedded Maghemite Nanoparticles , 2016 .

[43]  T. Russell,et al.  In situ grazing incidence small‐angle X‐ray scattering study of solvent vapor annealing in lamellae‐forming block copolymer thin films: Trade‐off of defects in deswelling , 2017 .

[44]  Matthias Opel,et al.  Printed Thin Magnetic Films Based on Diblock Copolymer and Magnetic Nanoparticles. , 2018, ACS applied materials & interfaces.

[45]  S. Roth,et al.  Spray‐Coating Magnetic Thin Hybrid Films of PS‐b‐PNIPAM and Magnetite Nanoparticles , 2019, Advanced Functional Materials.