Guided Assembly of Block Copolymers in Three-Dimensional Woodpile Scaffolds.

Three-dimensional (3D) nanofabrication using the directed self-assembly of block copolymers (BCPs) holds great promise for the nanoscale device fabrication and integration into 3D architectures over large areas with high element densities. In this work, a robust platform is developed for building 3D BCP architectures with tailored functionality using 3D micron-scale woodpile structures (WPSs), fabricated by a multiphoton polymerization technique. By completely filling the spaces of the WPSs and using the interactions of the blocks of the BCPs with the struts of the WPS, well-developed 3D nanoscopic morphologies are produced. Metal ion complexation with one block of the copolymer affords a convenient stain to highlight one of the microdomains of the copolymer for electron microscopy studies but also, with the reduction of the complexing salt to the corresponding metal, a simple strategy is shown to produce 3D constructs with nanoscopic domain resolution.

[1]  Joy Y. Cheng,et al.  Three‐Dimensional Nanofabrication by Block Copolymer Self‐Assembly , 2014, Advanced materials.

[2]  Seung Hwan Ko,et al.  Nanoscale Electronics: Digital Fabrication by Direct Femtosecond Laser Processing of Metal Nanoparticles , 2011, Advanced materials.

[3]  K. Ariga,et al.  Thin-film-based nanoarchitectures for soft matter: controlled assemblies into two-dimensional worlds. , 2011, Small.

[4]  Sang Woo Kim,et al.  Directed self-assembly of block copolymers in the extreme: guiding microdomains from the small to the large , 2013 .

[5]  C. Fotakis,et al.  Diffusion-assisted high-resolution direct femtosecond laser writing. , 2012, ACS nano.

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

[7]  Xiaodan Gu,et al.  High Aspect Ratio Sub‐15 nm Silicon Trenches From Block Copolymer Templates , 2012, Advanced materials.

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

[9]  Zhong Lin Wang,et al.  Large-Scale Hexagonal-Patterned Growth of Aligned ZnO Nanorods for Nano-optoelectronics and Nanosensor Arrays. , 2004, Nano letters.

[10]  K. W. Gotrik,et al.  3D TEM Tomography of Templated Bilayer Films of Block Copolymers , 2014 .

[11]  Xiangming Li,et al.  Toward Scalable Flexible Nanomanufacturing for Photonic Structures and Devices , 2016, Advanced materials.

[12]  F. Liu,et al.  Macroscopically ordered hexagonal arrays by directed self-assembly of block copolymers with minimal topographic patterns. , 2017, Nanoscale.

[13]  Ilker S. Bayer,et al.  Advances in top-down and bottom-up surface nanofabrication: techniques, applications & future prospects. , 2012, Advances in colloid and interface science.

[14]  Edwin L. Thomas,et al.  Monolayer films of diblock copolymer microdomains for nanolithographic applications , 1995, Journal of Materials Science.

[15]  C. Lieber,et al.  Nanowire Nanosensors for Highly Sensitive and Selective Detection of Biological and Chemical Species , 2001, Science.

[16]  Charles T. Black,et al.  Arbitrary lattice symmetries via block copolymer nanomeshes , 2015, Nature Communications.

[17]  Aifang Yu,et al.  An All‐Solid‐State Flexible Micro‐supercapacitor on a Chip , 2011 .

[18]  E. Kramer,et al.  Graphoepitaxy of Spherical Domain Block Copolymer Films , 2001 .

[19]  R. Ruiz,et al.  Density Multiplication and Improved Lithography by Directed Block Copolymer Assembly , 2008, Science.

[20]  Satoshi Kawata,et al.  Improved spatial resolution and surface roughness in photopolymerization-based laser nanowriting , 2005 .

[21]  T. Russell,et al.  Orthogonally Aligned Block Copolymer Line Patterns on Minimal Topographic Patterns. , 2018, ACS applied materials & interfaces.

[22]  Marc A. Hillmyer,et al.  High χ-Low N Block Polymers: How Far Can We Go? , 2015, ACS macro letters.

[23]  T. Russell,et al.  Directed Self-Assembly of Block Copolymer Thin Films Using Minimal Topographic Patterns. , 2016, ACS nano.

[24]  So Youn Kim,et al.  Large-area nanosquare arrays from shear-aligned block copolymer thin films. , 2014, Nano letters.

[25]  C. Fotakis,et al.  Ultra-low shrinkage hybrid photosensitive material for two-photon polymerization microfabrication. , 2008, ACS nano.

[26]  A. Piskarskas,et al.  Ultrafast laser nanostructuring of photopolymers: a decade of advances , 2013 .

[27]  Bumjoon J. Kim,et al.  Nanoparticle‐Induced Phase Transitions in Diblock‐Copolymer Films , 2005 .

[28]  G. Whitesides,et al.  Self-Assembly at All Scales , 2002, Science.

[29]  Satoshi Kawata,et al.  Finer features for functional microdevices , 2001, Nature.

[30]  T. Russell,et al.  Curving and Frustrating Flatland , 2004, Science.

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

[32]  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.

[33]  Jae Won Jeong,et al.  Nanotransfer printing with sub-10 nm resolution realized using directed self-assembly. , 2012, Advanced materials.

[34]  T. Russell,et al.  Evaluation of the Interaction Parameter for Poly(solketal methacrylate)-block-polystyrene Copolymers , 2018 .

[35]  Edwin L. Thomas,et al.  Competing Interactions and Levels of Ordering in Self-Organizing Polymeric Materials , 1997 .

[36]  Bong Hoon Kim,et al.  Flexible and Transferrable Self‐Assembled Nanopatterning on Chemically Modified Graphene , 2013, Advanced materials.

[37]  P. Nealey,et al.  Directed self-assembly of block copolymers on chemical patterns: A platform for nanofabrication , 2016 .

[38]  Satoshi Kawata,et al.  Two-photon laser precision microfabrication and its applications to micro-nano devices and systems , 2003 .

[39]  Kim Y. Lee,et al.  Directed Self‐Assembly of Poly(2‐vinylpyridine)‐b‐polystyrene‐b‐poly(2‐vinylpyridine) Triblock Copolymer with Sub‐15 nm Spacing Line Patterns Using a Nanoimprinted Photoresist Template , 2015, Advanced materials.

[40]  Nan Yao,et al.  Nanolithographic templates from diblock copolymer thin films , 1996 .

[41]  Joy Y. Cheng,et al.  Determination of the internal morphology of nanostructures patterned by directed self assembly. , 2014, ACS nano.

[42]  Charles M. Lieber,et al.  Nanoelectronics from the bottom up. , 2007, Nature materials.

[43]  K. W. Gotrik,et al.  Templating Three-Dimensional Self-Assembled Structures in Bilayer Block Copolymer Films , 2012, Science.

[44]  Bharat Bhushan,et al.  Hydrophobicity, adhesion, and friction properties of nanopatterned polymers and scale dependence for micro- and nanoelectromechanical systems. , 2005, Nano letters.

[45]  Juan J de Pablo,et al.  Characterizing the Three-Dimensional Structure of Block Copolymers via Sequential Infiltration Synthesis and Scanning Transmission Electron Tomography. , 2015, ACS nano.

[46]  Yong Wang,et al.  Nanoporous Metal Membranes with Bicontinuous Morphology from Recyclable Block‐Copolymer Templates , 2010, Advanced materials.

[47]  Shu Yang,et al.  Stability of high-aspect-ratio micropillar arrays against adhesive and capillary forces. , 2010, Accounts of chemical research.

[48]  K. A. Brown,et al.  Progress in Top-Down Control of Bottom-Up Assembly. , 2017, Nano letters.

[49]  Ralu Divan,et al.  Quantitative Three-Dimensional Characterization of Block Copolymer Directed Self-Assembly on Combined Chemical and Topographical Prepatterned Templates. , 2017, ACS nano.