Entropy driven spontaneous formation of highly porous films from polymer–nanoparticle composites

Nanoporous materials have become indispensable in many fields ranging from photonics, catalysis and semiconductor processing to biosensor infrastructure. Rapid and energy efficient process fabrication of these materials is, however, nontrivial. In this communication, we describe a simple method for the rapid fabrication of these materials from colloidal dispersions of Polymethyl Silsesquioxane nanoparticles. Nanoparticle-polymer composites above the decomposition temperature of the polymer are examined and the entropic gain experienced by the nanoparticles in this rubric is harnessed to fabricate novel highly porous films composed of nanoparticles. Optically smooth, hydrophobic films with low refractive indices (as low as 1.048) and high surface areas (as high as 1325 m(2) g(-1)) have been achieved with this approach. In this communication we address the behavior of such systems that are both temperature and substrate surface energy dependent. The method is applicable, in principle, to a variety of nanoparticle-polymer systems to fabricate custom nanoporous materials.

[1]  Bumjoon J. Kim,et al.  Control of nanoparticle location in block copolymers. , 2005, Journal of the American Chemical Society.

[2]  Anna C. Balazs,et al.  Using nanocomposite coatings to heal surface defects , 2004 .

[3]  Jun Liu,et al.  Low dielectric constant mesoporous silica films through molecularly templated synthesis , 2000 .

[4]  T. Baumann,et al.  Structure of low-density nanoporous dielectrics revealed by low-vacuum electron microscopy and small-angle X-ray scattering. , 2007, Langmuir.

[5]  G. Raos,et al.  Macromolecular clusters in poor-solvent polymer solutions , 1997 .

[6]  Sol M Gruner,et al.  Ordered Mesoporous Materials from Metal Nanoparticle–Block Copolymer Self-Assembly , 2008, Science.

[7]  P. Rice,et al.  Supercritical carbon dioxide extraction of porogens for the preparation of ultralow-dielectric-constant films , 2003 .

[8]  A. Balazs,et al.  Predicting the Mesophases of Copolymer-Nanoparticle Composites , 2001, Science.

[9]  Jinhwan Yoon,et al.  Imprinting well-controlled closed-nanopores in spin-on polymeric dielectric thin films , 2006 .

[10]  Wen‐Chang Chen,et al.  Low dielectric constant nanoporous poly(methyl silsesquioxane) using poly(styrene-block-2-vinylpyridine) as a template , 2004 .

[11]  H. Militz,et al.  Surface Energy Determinations of Wood: Comparison of Methods and Wood Species , 2000 .

[12]  David S. Germack,et al.  A facile approach to architecturally defined nanoparticles via intramolecular chain collapse. , 2002, Journal of the American Chemical Society.

[13]  Koushik Biswas,et al.  Nanoporous organosilicate films as antireflection coatings , 2006 .

[14]  Janos Veres,et al.  Low‐k Insulators as the Choice of Dielectrics in Organic Field‐Effect Transistors , 2003 .

[15]  Arnold A. Lubguban,et al.  Characterization of porous low-k films using variable angle spectroscopic ellipsometry , 2006 .

[16]  W. Risk,et al.  Optical waveguides with an aqueous core and a low-index nanoporous cladding. , 2004, Optics express.

[17]  Anna C Balazs,et al.  Using nanoparticles to create self-healing composites. , 2004, The Journal of chemical physics.

[18]  W. Oh,et al.  Ultralow-k nanoporous organosilicate dielectric films imprinted with dendritic spheres , 2005, Nature materials.

[19]  Anna C. Balazs,et al.  Entropy-driven segregation of nanoparticles to cracks in multilayered composite polymer structures , 2006 .

[20]  E. Fred Schubert,et al.  Low-refractive-index materials - A new class of optical thin-film materials , 2007, 2009 Conference on Lasers and Electro-Optics and 2009 Conference on Quantum electronics and Laser Science Conference.

[21]  Masatsugu Shimomura,et al.  Spontaneous formation of polymer nanoparticles by good-solvent evaporation as a nonequilibrium process. , 2005, Chaos.

[22]  M. Mackay,et al.  Improved polymer thin-film wetting behavior through nanoparticle segregation to interfaces , 2007 .

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

[24]  Yunfeng Lu,et al.  Evaporation-Induced Self-Assembly: Nanostructures Made Easy** , 1999 .

[25]  Cortney R. Kreller,et al.  Fabrication of Multilayered Nanoporous Poly(methyl silsesquioxane) , 2002 .

[26]  Hyunhyub Ko,et al.  Porous substrates for label-free molecular level detection of nonresonant organic molecules. , 2009, ACS nano.

[27]  Rasmus Niemi,et al.  Targeting of porous hybrid silica nanoparticles to cancer cells. , 2009, ACS nano.

[28]  P. Duxbury,et al.  Self-assembled multilayers of nanocomponents. , 2007, Nano letters.

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

[30]  Ultra‐low Refractive Index Mesoporous Substrates for Waveguide Structures , 2008 .

[31]  Karen Maex,et al.  Low dielectric constant materials for microelectronics , 2003 .

[32]  Jackie Y. Ying,et al.  Nanostructural tailoring: Opportunities for molecular engineering in catalysis , 2000 .