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      Directed Self-Assembly of Diamond Networks in Triblock Terpolymer Films on Patterned Substrates

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          Abstract

          Block copolymers (BCPs) are particularly effective in creating soft nanostructured templates for transferring complex 3D network structures into inorganic materials that are difficult to fabricate by other methods. However, achieving control of the local ordering within these 3D networks over large areas remains a significant obstacle to advancing material properties. Here, we address this challenge by directing the self-assembly of a 3D alternating diamond morphology by solvent vapor annealing of a triblock terpolymer film on a chemically patterned substrate. The hexagonal substrate patterns were designed to match a (111) plane of the diamond lattice. Commensurability between the sparse substrate pattern and the BCP lattice produced a uniformly ordered diamond network within the polymer film, as confirmed by a combination of atomic force microscopy and cross-sectional imaging using focused ion beam scanning electron microscopy. The successful replication of the complex and well-ordered 3D network structure in gold promises to advance optical metamaterials and has potential applications in nanophotonics.

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          Density multiplication and improved lithography by directed block copolymer assembly.

          Self-assembling materials spontaneously form structures at length scales of interest in nanotechnology. In the particular case of block copolymers, the thermodynamic driving forces for self-assembly are small, and low-energy defects can get easily trapped. We directed the assembly of defect-free arrays of isolated block copolymer domains at densities up to 1 terabit per square inch on chemically patterned surfaces. In comparing the assembled structures to the chemical pattern, the density is increased by a factor of four, the size is reduced by a factor of two, and the dimensional uniformity is vastly improved.
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            50th Anniversary Perspective: Block Polymers—Pure Potential

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              Nanostructure engineering by templated self-assembly of block copolymers.

              Self-assembling materials are the building blocks for bottom-up nanofabrication processes, but many self-assembled nanostructures contain defects and lack sufficient long-range order for certain nanotechnology applications. Here we investigate the formation of defects in a self-assembled array of spherical block-copolymer microdomains, using topographical templates to control the local self-assembly. Perfect ordered sphere arrays can form in both constant-width templates and width-modulated templates. For modulated templates, transition between configurations having a constant number of rows and configurations of stable arrays with varying numbers of rows is shown to be analogous to dislocation formation in an epitaxial thin film system. Based on the configuration transition energy and fluctuation energy, designed templates with a high tolerance for lithographical imperfections can direct precisely modulated block-copolymer nanostructures. This study provides insights into the design of hybrid systems combining top-down and bottom-up fabrication.
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                Author and article information

                Journal
                ACS Appl Mater Interfaces
                ACS Appl Mater Interfaces
                am
                aamick
                ACS Applied Materials & Interfaces
                American Chemical Society
                1944-8244
                1944-8252
                21 November 2023
                20 December 2023
                : 15
                : 50 , Block Copolymers: Building Block for Next Generation Nanotechnology
                : 57981-57991
                Affiliations
                []Adolphe Merkle Institute, University of Fribourg , Chemin des Verdiers 4, 1700 Fribourg, Switzerland
                []Laboratory for Nanoelectronics and Spintronics, Research Institute of Electrical Communication, Tohoku University , 2-1-1 Katahira, Aoba-ku, Sendai 980-8577, Japan
                []WPI Advanced Institute for Materials Research, Tohoku University , 2-1-1 Katahira, Aoba-ku, Sendai 980-8577, Japan
                [§ ]Center for Science and Innovation in Spintronics, Tohoku University , 2-1-1 Katahira, Aoba-ku, Sendai 980-8577, Japan
                []Center for Innovative Integrated Electronic Systems, Tohoku University , 468-1 Aramaki Aza Aoba, Aoba-ku, Sendai 980-0845, Japan
                []Inamori Research Institute for Science , Kyoto 600-8411, Japan
                [# ]Department of Materials Science and Engineering, Cornell University , 214 Bard Hall, Ithaca, New York 14853-1501, United States
                [@ ]Department of Chemistry and Physics of Materials, University of Salzburg , Jakob-Haringer-Str. 2a, Salzburg 5020, Austria
                []Swiss National Center of Competence in Research (NCCR) Bio-Inspired Materials, University of Fribourg , Chemin des Verdiers 4, 1700 Fribourg, Switzerland
                Author notes
                Author information
                https://orcid.org/0000-0002-4268-2148
                https://orcid.org/0000-0001-6934-3755
                https://orcid.org/0000-0002-2727-7128
                https://orcid.org/0000-0001-5936-339X
                https://orcid.org/0000-0002-1362-6083
                https://orcid.org/0000-0001-5738-5309
                Article
                10.1021/acsami.3c10619
                10739600
                37989271
                f75868bd-103a-48e4-a8bc-3ccbcd58f578
                © 2023 The Authors. Published by American Chemical Society

                Permits the broadest form of re-use including for commercial purposes, provided that author attribution and integrity are maintained ( https://creativecommons.org/licenses/by/4.0/).

                History
                : 20 July 2023
                : 17 October 2023
                : 13 October 2023
                Funding
                Funded by: Schweizerischer Nationalfonds zur Förderung der Wissenschaftlichen Forschung, doi 10.13039/501100001711;
                Award ID: 188647
                Funded by: Adolphe Merkle Foundation, doi 10.13039/501100003071;
                Award ID: NA
                Categories
                Forum Article
                Custom metadata
                am3c10619
                am3c10619

                Materials technology
                block copolymer self-assembly,alternating diamond,chemical patterning,solvent vapor annealing,templated fabrication,nanostructured single diamond gold networks

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