Sub‐Nanometer Level Size Tuning of a Monodisperse Nanoparticle Array Via Block Copolymer Lithography

The fabrication and catalytic application of a size-tunable monodisperse nanoparticle array enabled by block copolymer lithography is demonstrated. Highly uniform vertical cylinder nanodomains are achieved in poly(styrene-block-4-vinylpyridine) (PS-b-P4VP) diblock copolymer thin-films by solvent annealing. The prominent diffusion of the anionic metal complexes into the protonated P4VP cylinder nanodomains occurs through specific electrostatic interactions in a weakly acidic aqueous solution. This well-defined diffusion with nanoscale confinement enables preparation of the laterally ordered monodisperse nanoparticle array with sub-nanometer level precise size tuning. The controlled growth of monodisperse nanoparticle arrays is proven by their catalytic use for vertical carbon nanotube (CNT) growth via plasma enhanced chemical vapor deposition (PECVD). Since the size of the catalyst particles is the decisive parameter for the diameters and wall-numbers of CNTs, the highly selective growth of double-walled or triple-walled CNTs could be accomplished using monodisperse nanoparticle arrays.

[1]  Sang Ouk Kim,et al.  Highly efficient vertical growth of wall-number-selected, N-doped carbon nanotube arrays. , 2009, Nano letters.

[2]  Xiaoming Yang,et al.  Directed self-assembly of cylinder-forming block copolymers: prepatterning effect on pattern quality and density multiplication factor. , 2009, Langmuir : the ACS journal of surfaces and colloids.

[3]  Tae Hee Han,et al.  A plasmonic biosensor array by block copolymer lithography , 2010 .

[4]  Joel K. W. Yang,et al.  Graphoepitaxy of Self-Assembled Block Copolymers on Two-Dimensional Periodic Patterned Templates , 2008, Science.

[5]  D. Weller,et al.  Directed Block Copolymer Assembly versus Electron Beam Lithography for Bit-Patterned Media with Areal Density of 1 Terabit/inch(2) and Beyond. , 2009, ACS nano.

[6]  Hege S. Beard,et al.  Photochemistry of ketones adsorbed on size/shape selective zeolites. A supramolecular approach to persistent carbon centered radicals , 1998 .

[7]  Koji Asakawa,et al.  2.5-inch disk patterned media prepared by an artificially assisted self-assembling method , 2002 .

[8]  V. Zhdanov,et al.  Specifics of substrate-mediated photo-induced chemical processes on supported nm-sized metal particles , 2004 .

[9]  M. Beard,et al.  Electronic Coupling in InP Nanoparticle Arrays , 2003 .

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

[11]  U. Simon,et al.  Gold nanoparticles: assembly and electrical properties in 1-3 dimensions. , 2005, Chemical Communications.

[12]  F. Caruso,et al.  Layer-by-layer assembled charge-trap memory devices with adjustable electronic properties. , 2007, Nature nanotechnology.

[13]  Christopher Harrison,et al.  Block copolymer lithography: Periodic arrays of ~1011 holes in 1 square centimeter , 1997 .

[14]  K. Guarini,et al.  Ultrahigh-density nanowire arrays grown in self-assembled diblock copolymer templates. , 2000, Science.

[15]  R. Ho,et al.  Fabrication of Double‐Length‐Scale Patterns via Lithography, Block Copolymer Templating, and Electrodeposition , 2007 .

[16]  Soojin Park,et al.  Macroscopic 10-Terabit–per–Square-Inch Arrays from Block Copolymers with Lateral Order , 2009, Science.

[17]  Jillian M. Buriak,et al.  Block Copolymer Templated Chemistry for the Formation of Metallic Nanoparticle Arrays on Semiconductor Surfaces , 2007 .

[18]  A Imre,et al.  Majority Logic Gate for Magnetic Quantum-Dot Cellular Automata , 2006, Science.

[19]  P. Simon,et al.  Fungal templates for noble-metal nanoparticles and their application in catalysis. , 2008, Angewandte Chemie.

[20]  Bong Hoon Kim,et al.  Hierarchical Self‐Assembly of Block Copolymers for Lithography‐Free Nanopatterning , 2008 .

[21]  Soojin Park,et al.  Ordering of PS-b-P4VP on patterned silicon surfaces. , 2008, ACS nano.

[22]  O. Hellwig,et al.  Bit patterned media based on block copolymer directed assembly with narrow magnetic switching field distribution , 2010 .

[23]  Erin M. Lennon,et al.  Evolution of Block Copolymer Lithography to Highly Ordered Square Arrays , 2008, Science.

[24]  Ying Zhang,et al.  Polymer self assembly in semiconductor microelectronics , 2006, 2006 International Electron Devices Meeting.

[25]  J. Jung,et al.  Directed self-assembly of two kinds of nanoparticles utilizing monolayer films of diblock copolymer micelles. , 2003, Journal of the American Chemical Society.

[26]  Bong Hoon Kim,et al.  Block copolymer multiple patterning integrated with conventional ArF lithography , 2010 .

[27]  H. Dai,et al.  Self-oriented regular arrays of carbon nanotubes and their field emission properties , 1999, Science.

[28]  Bong Hoon Kim,et al.  One-Dimensional Nanoassembly of Block Copolymers Tailored by Chemically Patterned Surfaces , 2009 .

[29]  Mostafa A. El-Sayed,et al.  Shape-Dependent Catalytic Activity of Platinum Nanoparticles in Colloidal Solution , 2004 .

[30]  Dong Ok Shin,et al.  Hierarchically Organized Carbon Nanotube Arrays from Self‐Assembled Block Copolymer Nanotemplates , 2008 .

[31]  W. P. Hall,et al.  A Localized Surface Plasmon Resonance Biosensor: First Steps toward an Assay for Alzheimer's Disease , 2004 .

[32]  L. Manna,et al.  Metal-enhanced fluorescence of colloidal nanocrystals with nanoscale control , 2006, Nature nanotechnology.

[33]  Satoru Suzuki,et al.  Single-walled carbon nanotube growth from highly activated metal nanoparticles. , 2006, Nano letters.

[34]  P. Nealey,et al.  Epitaxial self-assembly of block copolymers on lithographically defined nanopatterned substrates , 2003, Nature.

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

[36]  Sang-Won Kang,et al.  Universal Block Copolymer Lithography for Metals, Semiconductors, Ceramics, and Polymers , 2008 .

[37]  R. Ruoff,et al.  Versatile Carbon Hybrid Films Composed of Vertical Carbon Nanotubes Grown on Mechanically Compliant Graphene Films , 2010, Advanced materials.

[38]  Zhe Yuan,et al.  Plasmonic properties of supported Pt and Pd nanostructures. , 2006, Nano letters.

[39]  Soojin Park,et al.  From nanorings to nanodots by patterning with block copolymers. , 2008, Nano letters.

[40]  N. McIntyre,et al.  X-ray photoelectron spectroscopic studies of iron oxides , 1977 .

[41]  Sun,et al.  Monodisperse FePt nanoparticles and ferromagnetic FePt nanocrystal superlattices , 2000, Science.