Selective sequential infiltration synthesis of ZnO in the liquid crystalline phase of silicon-containing rod-coil block copolymers

Shi, Ling-Ying; Subramanian, Ashwanth; Weng, Lin; Lee, Sangho; Kisslinger, Kim; Nam, Chang-Yong; Ross, Caroline A.

doi:10.1039/d1nr06065a

Selective sequential infiltration synthesis of ZnO in the liquid crystalline phase of silicon-containing rod-coil block copolymers

Journal Article · Thu Jan 06 23:00:00 EST 2022 · Nanoscale

DOI:https://doi.org/10.1039/d1nr06065a· OSTI ID:1854495

^[1]; ^[2]; Weng, Lin ^[3]; ^[4]; Kisslinger, Kim ^[5]; ^[6]; ^[4]

Sichuan Univ., Chengdu (China); Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
Stony Brook Univ., NY (United States)
Sichuan Univ., Chengdu (China)
Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN)
Stony Brook Univ., NY (United States); Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN)

The combination of block copolymer (BCP) thin film self-assembly and selective infiltration synthesis of inorganic materials into one BCP block provides access to various organic–inorganic hybrids. Here, we apply sequential infiltration synthesis, a vapor-phase hybridization technique, to selectively introduce ZnO into the organic microdomains of silicon-containing rod-coil diblock copolymers and a triblock terpolymer, polydimethylsiloxane (PDMS)-b-poly{2,5-bis[(4-methoxyphenyl)-oxycarbonyl]styrene} (PDMS-b-PMPCS) and PDMS-b-polystyrene-b-PMPCS (PDMS-b-PS-b-PMPCS), in which the PMPCS rod block is a liquid crystalline polymer. The in-plane cylindrical PDMS-b-PMPCS and core–shell cylindrical and hexagonally perforated lamellar PDMS-b-PS-b-PMPCS films were infiltrated with ZnO with high selectivity to the PMPCS. The etching contrast between PDMS, PS and the ZnO-infused PMPCS enables the fabrication of ZnO/SiO_x binary composites by plasma etching and reveals the core–shell morphology of the triblock terpolymer.

View Accepted Manuscript (DOE)

Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); National Science Foundation (NSF); Applied Basic Research Program of Science and Technology Commission Foundation of Sichuan Province

Grant/Contract Number:: SC0012704

OSTI ID:: 1854495

Report Number(s):: BNL-222826-2022-JAAM

Journal Information:: Nanoscale, Journal Name: Nanoscale Journal Issue: 5 Vol. 14; ISSN 2040-3364

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

References (40)

Nanoscopic Patterned Materials with Tunable Dimensions via Atomic Layer Deposition on Block Copolymers Peng, Qing; Tseng, Yu-Chih; Darling, Seth B. Advanced Materials, Vol. 22, Issue 45, p. 5129-5133 https://doi.org/10.1002/adma.201002465	journal	September 2010
Sub-10 nm Features Obtained from Directed Self-Assembly of Semicrystalline Polycarbosilane-Based Block Copolymer Thin Films Aissou, Karim; Mumtaz, Muhammad; Fleury, Guillaume Advanced Materials, Vol. 27, Issue 2 https://doi.org/10.1002/adma.201404077	journal	November 2014
Strategies for Inorganic Incorporation using Neat Block Copolymer Thin Films for Etch Mask Function and Nanotechnological Application Cummins, Cian; Ghoshal, Tandra; Holmes, Justin D. Advanced Materials, Vol. 28, Issue 27 https://doi.org/10.1002/adma.201503432	journal	January 2016
3D Tailored Crumpling of Block-Copolymer Lithography on Chemically Modified Graphene Kim, Ju Young; Lim, Joonwon; Jin, Hyeong Min Advanced Materials, Vol. 28, Issue 8 https://doi.org/10.1002/adma.201504590	journal	December 2015
Directed Self‐Assembly of Liquid‐Crystalline Molecular Building Blocks for Sub‐5 nm Nanopatterning Nickmans, Koen; Schenning, Albert P. H. J. Advanced Materials, Vol. 30, Issue 3 https://doi.org/10.1002/adma.201703713	journal	October 2017
Head-Tail Asymmetry as the Determining Factor in the Formation of Polymer Cubosomes or Hexasomes in a Rod-Coil Amphiphilic Block Copolymer Lyu, Xiaolin; Xiao, Anqi; Zhang, Wei Angewandte Chemie International Edition, Vol. 57, Issue 32 https://doi.org/10.1002/anie.201804401	journal	July 2018
Laterally Ordered Sub-10 nm Features Obtained From Directed Self-Assembly of Si-Containing Block Copolymer Thin Films Rho, Yecheol; Aissou, Karim; Mumtaz, Muhammad Small, Vol. 11, Issue 48 https://doi.org/10.1002/smll.201500439	journal	November 2015
Highly Ordered Nanoring Arrays Formed by Templated Si-Containing Triblock Terpolymer Thin Films Aissou, Karim; Mumtaz, Muhammad; Marcasuzaa, Pierre Small, Vol. 13, Issue 12 https://doi.org/10.1002/smll.201603184	journal	January 2017
Synthesis and self-assembly of a linear coil-coil-rod ABC triblock copolymer Shi, Ling-ying; Pan, Yu; Zhang, Qi-kai Chinese Journal of Polymer Science, Vol. 32, Issue 11 https://doi.org/10.1007/s10118-014-1533-7	journal	September 2014
Review of Recent Advances in Applications of Vapor-Phase Material Infiltration Based on Atomic Layer Deposition Subramanian, Ashwanth; Tiwale, Nikhil; Nam, Chang-Yong JOM, Vol. 71, Issue 1 https://doi.org/10.1007/s11837-018-3141-4	journal	September 2018
Directing the self-assembly of block copolymers Darling, S. B. Progress in Polymer Science, Vol. 32, Issue 10 https://doi.org/10.1016/j.progpolymsci.2007.05.004	journal	October 2007
Silicon-containing block copolymers for lithographic applications Lo, Ting-Ya; Krishnan, Mohan Raj; Lu, Kai-Yuan Progress in Polymer Science, Vol. 77 https://doi.org/10.1016/j.progpolymsci.2017.10.002	journal	February 2018
Resolving Triblock Terpolymer Morphologies by Vapor-Phase Infiltration Lee, Sangho; Subramanian, Ashwanth; Tiwale, Nikhil Chemistry of Materials, Vol. 32, Issue 12 https://doi.org/10.1021/acs.chemmater.0c01647	journal	May 2020
Directing Hybrid Structures by Combining Self-Assembly of Functional Block Copolymers and Atomic Layer Deposition: A Demonstration on Hybrid Photovoltaics Moshonov, Moshe; Frey, Gitti L. Langmuir, Vol. 31, Issue 46 https://doi.org/10.1021/acs.langmuir.5b03282	journal	November 2015
Annealing Process Dependence of the Self-Assembly of Rod–Coil Block Copolymer Thin Films Shi, Ling-Ying; Yin, Chengxiao; Zhou, Bo Macromolecules, Vol. 54, Issue 4 https://doi.org/10.1021/acs.macromol.0c02712	journal	February 2021
In Situ Characterization of the Self-Assembly of a Polystyrene–Polydimethylsiloxane Block Copolymer during Solvent Vapor Annealing Bai, W.; Yager, K. G.; Ross, C. A. Macromolecules, Vol. 48, Issue 23 https://doi.org/10.1021/acs.macromol.5b02174	journal	November 2015
Templated Self-Assembly of a PS- Branch -PDMS Bottlebrush Copolymer Cheng, Li-Chen; Gadelrab, Karim R.; Kawamoto, Ken Nano Letters, Vol. 18, Issue 7 https://doi.org/10.1021/acs.nanolett.8b01389	journal	June 2018
Self-Assembly of Complex Multimetal Nanostructures from Perforated Lamellar Block Copolymer Thin Films Cha, Seung Keun; Lee, Gil Yong; Mun, Jeong Ho ACS Applied Materials & Interfaces, Vol. 9, Issue 18 https://doi.org/10.1021/acsami.7b03319	journal	April 2017
Enhanced Hybridization and Nanopatterning via Heated Liquid-Phase Infiltration into Self-Assembled Block Copolymer Thin Films Subramanian, Ashwanth; Tiwale, Nikhil; Doerk, Gregory ACS Applied Materials & Interfaces, Vol. 12, Issue 1 https://doi.org/10.1021/acsami.9b16148	journal	December 2019
High χ–Low N Block Polymers: How Far Can We Go? Sinturel, Christophe; Bates, Frank S.; Hillmyer, Marc A. ACS Macro Letters, Vol. 4, Issue 9 https://doi.org/10.1021/acsmacrolett.5b00472	journal	September 2015
Core–Shell and Zigzag Nanostructures from a Thin Film Silicon-Containing Conformationally Asymmetric Triblock Terpolymer Shi, Ling-Ying; Liao, Fen; Cheng, Li-Chen ACS Macro Letters, Vol. 8, Issue 7 https://doi.org/10.1021/acsmacrolett.9b00283	journal	June 2019
Au–Ag Core–Shell Nanoparticle Array by Block Copolymer Lithography for Synergistic Broadband Plasmonic Properties Cha, Seung Keun; Mun, Jeong Ho; Chang, Taeyong ACS Nano, Vol. 9, Issue 5 https://doi.org/10.1021/acsnano.5b01641	journal	April 2015
Conformal 3D Nanopatterning by Block Copolymer Lithography with Vapor-Phase Deposited Neutral Adlayer Yang, Geon Gug; Choi, Junhwan; Cha, Seung Keun ACS Nano, Vol. 13, Issue 11 https://doi.org/10.1021/acsnano.9b05859	journal	October 2019
Vertical Lamellae Formed by Two-Step Annealing of a Rod–Coil Liquid Crystalline Block Copolymer Thin Film Shi, Ling-Ying; Lan, Ji; Lee, Sangho ACS Nano, Vol. 14, Issue 4 https://doi.org/10.1021/acsnano.9b09702	journal	March 2020
Block Copolymer Templated Chemistry for the Formation of Metallic Nanoparticle Arrays on Semiconductor Surfaces Aizawa, Masato; Buriak, Jillian M. Chemistry of Materials, Vol. 19, Issue 21 https://doi.org/10.1021/cm071382b	journal	October 2007
Temperature-Dependent Infiltration of Polymers during Sequential Exposures to Trimethylaluminum Padbury, Richard P.; Jur, Jesse S. Langmuir, Vol. 30, Issue 30 https://doi.org/10.1021/la501679f	journal	July 2014
Remarkably Rich Variety of Nanostructures and Order–Order Transitions in a Rod–Coil Diblock Copolymer Shi, Ling-Ying; Zhou, Yu; Fan, Xing-He Macromolecules, Vol. 46, Issue 13 https://doi.org/10.1021/ma400944z	journal	June 2013
Highly Tunable Self-Assembled Nanostructures from a Poly(2-vinylpyridine- b -dimethylsiloxane) Block Copolymer Jeong, Jae Won; Park, Woon Ik; Kim, Mi-Jeong Nano Letters, Vol. 11, Issue 10 https://doi.org/10.1021/nl2016224	journal	October 2011
A Route to Nanoscopic Materials via Sequential Infiltration Synthesis on Block Copolymer Templates Peng, Qing; Tseng, Yu-Chih; Darling, Seth B. ACS Nano, Vol. 5, Issue 6, p. 4600-4606 https://doi.org/10.1021/nn2003234	journal	May 2011
Chemically Enhancing Block Copolymers for Block-Selective Synthesis of Self-Assembled Metal Oxide Nanostructures Kamcev, Jovan; Germack, David S.; Nykypanchuk, Dmytro ACS Nano, Vol. 7, Issue 1 https://doi.org/10.1021/nn304122b	journal	December 2012
Nanoporous Block Copolymer Membranes for Ultrafiltration: A Simple Approach to Size Tunability Ahn, Hyungju; Park, Sungmin; Kim, Sang-Woo ACS Nano, Vol. 8, Issue 11 https://doi.org/10.1021/nn505234v	journal	November 2014
Non-native three-dimensional block copolymer morphologies Rahman, Atikur; Majewski, Pawel W.; Doerk, Gregory Nature Communications, Vol. 7, Issue 1 https://doi.org/10.1038/ncomms13988	journal	December 2016
Assembly of aligned linear metallic patterns on silicon Chai, Jinan; Wang, Dong; Fan, Xiangning Nature Nanotechnology, Vol. 2, Issue 8 https://doi.org/10.1038/nnano.2007.227	journal	August 2007
Highly ordered TiO ₂ nanostructures by sequential vapour infiltration of block copolymer micellar films in an atomic layer deposition reactor Yin, Jun; Xu, Qiang; Wang, Zhaogen J. Mater. Chem. C, Vol. 1, Issue 5 https://doi.org/10.1039/C2TC00306F	journal	January 2013
The use of atomic layer deposition in advanced nanopatterning Mackus, A. J. M.; Bol, A. A.; Kessels, W. M. M. Nanoscale, Vol. 6, Issue 19 https://doi.org/10.1039/C4NR01954G	journal	January 2014
Three-dimensional electroactive ZnO nanomesh directly derived from hierarchically self-assembled block copolymer thin films Subramanian, Ashwanth; Doerk, Gregory; Kisslinger, Kim Nanoscale, Vol. 11, Issue 19 https://doi.org/10.1039/C9NR00206E	journal	January 2019
Mesogen-jacketed liquid crystalline polymers Chen, Xiao-Fang; Shen, Zhihao; Wan, Xin-Hua Chemical Society Reviews, Vol. 39, Issue 8 https://doi.org/10.1039/b814540g	journal	January 2010
Emerging trends in metal-containing block copolymers: synthesis, self-assembly, and nanomanufacturing applications Ramanathan, Muruganathan; Tseng, Yu-Chih; Ariga, Katsuhiko Journal of Materials Chemistry C, Vol. 1, Issue 11 https://doi.org/10.1039/c3tc00930k	journal	January 2013
Block Copolymers—Designer Soft Materials Bates, Frank S.; Fredrickson, Glenn H. Physics Today, Vol. 52, Issue 2 https://doi.org/10.1063/1.882522	journal	February 1999
Templating Three-Dimensional Self-Assembled Structures in Bilayer Block Copolymer Films Tavakkoli K. G., A.; Gotrik, K. W.; Hannon, A. F. Science, Vol. 336, Issue 6086 https://doi.org/10.1126/science.1218437	journal	June 2012

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36 MATERIALS SCIENCE
microphase separation
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Selective sequential infiltration synthesis of ZnO in the liquid crystalline phase of silicon-containing rod-coil block copolymers

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