Self-assembly of a silicon-containing side-chain liquid crystalline block copolymer in bulk and in thin films: kinetic pathway of a cylinder to sphere transition
The self-assembly of a high-χ silicon-containing side-chain liquid crystalline block copolymer (LC BCP) in bulk and in thin films is reported, and the structural transition process from the hexagonally packed cylinder (HEX) to the body-centered cubic structure (BCC) in thin films was examined by bot...
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Royal Society of Chemistry
2019
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| Online Access: | http://hdl.handle.net/1721.1/120168 https://orcid.org/0000-0001-9975-9903 https://orcid.org/0000-0003-4164-1827 https://orcid.org/0000-0003-2262-1249 |
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| author | Liao, Fen Ran, Rong Yager, Kevin G. Shi, Lingying Cheng, Li-Chen Lee, Sangho Ross, Caroline A |
| author2 | Massachusetts Institute of Technology. Department of Materials Science and Engineering |
| author_facet | Massachusetts Institute of Technology. Department of Materials Science and Engineering Liao, Fen Ran, Rong Yager, Kevin G. Shi, Lingying Cheng, Li-Chen Lee, Sangho Ross, Caroline A |
| author_sort | Liao, Fen |
| collection | MIT |
| description | The self-assembly of a high-χ silicon-containing side-chain liquid crystalline block copolymer (LC BCP) in bulk and in thin films is reported, and the structural transition process from the hexagonally packed cylinder (HEX) to the body-centered cubic structure (BCC) in thin films was examined by both reciprocal and real space experimental methods. The block copolymer, poly(dimethylsiloxane-b-11-(4′-cyanobiphenyl-4-yloxy)undecylmethacrylate) (PDMS-b-P(4CNB11C)MA) with a molecular weight of 19.5 kg mol−1 and a volume fraction of PDMS 27% self-assembled in bulk into a hierarchical nanostructure of sub-20 nm HEX cylinders of PDMS with the P(4CNB11C)MA block exhibiting a smectic LC phase with a 1.61 nm period. The structure remained HEX as the P(4CNB11C)MA block transformed to an isotropic phase at ∼120 °C. In the thin films, the PDMS cylindrical microdomains were oriented in layers parallel to the substrate surface. The LC block formed a smectic LC phase which transformed to an isotropic phase at ∼120 °C, and the microphase-separated nanostructure transformed from HEX to BCC spheres at ∼160 °C. The hierarchical structure as well as the dynamic structural transition of the thin films were characterized using in situ grazing-incidence small-angle X-ray scattering and grazing-incidence wide-angle X-ray scattering. The transient morphologies from the HEX to BCC structure in thin films were captured by scanning electron microscopy and atomic force microscopy, and the transition pathway was described. |
| first_indexed | 2024-09-23T09:12:39Z |
| format | Article |
| id | mit-1721.1/120168 |
| institution | Massachusetts Institute of Technology |
| last_indexed | 2024-09-23T09:12:39Z |
| publishDate | 2019 |
| publisher | Royal Society of Chemistry |
| record_format | dspace |
| spelling | mit-1721.1/1201682022-09-26T11:05:16Z Self-assembly of a silicon-containing side-chain liquid crystalline block copolymer in bulk and in thin films: kinetic pathway of a cylinder to sphere transition Liao, Fen Ran, Rong Yager, Kevin G. Shi, Lingying Cheng, Li-Chen Lee, Sangho Ross, Caroline A Massachusetts Institute of Technology. Department of Materials Science and Engineering Shi, Lingying Cheng, Li-Chen Lee, Sangho Ross, Caroline A The self-assembly of a high-χ silicon-containing side-chain liquid crystalline block copolymer (LC BCP) in bulk and in thin films is reported, and the structural transition process from the hexagonally packed cylinder (HEX) to the body-centered cubic structure (BCC) in thin films was examined by both reciprocal and real space experimental methods. The block copolymer, poly(dimethylsiloxane-b-11-(4′-cyanobiphenyl-4-yloxy)undecylmethacrylate) (PDMS-b-P(4CNB11C)MA) with a molecular weight of 19.5 kg mol−1 and a volume fraction of PDMS 27% self-assembled in bulk into a hierarchical nanostructure of sub-20 nm HEX cylinders of PDMS with the P(4CNB11C)MA block exhibiting a smectic LC phase with a 1.61 nm period. The structure remained HEX as the P(4CNB11C)MA block transformed to an isotropic phase at ∼120 °C. In the thin films, the PDMS cylindrical microdomains were oriented in layers parallel to the substrate surface. The LC block formed a smectic LC phase which transformed to an isotropic phase at ∼120 °C, and the microphase-separated nanostructure transformed from HEX to BCC spheres at ∼160 °C. The hierarchical structure as well as the dynamic structural transition of the thin films were characterized using in situ grazing-incidence small-angle X-ray scattering and grazing-incidence wide-angle X-ray scattering. The transient morphologies from the HEX to BCC structure in thin films were captured by scanning electron microscopy and atomic force microscopy, and the transition pathway was described. National Science Foundation (U.S.) (DMR-1606911) National Natural Science Foundation (China) (Grant 51403132) National Natural Science Foundation (China) (Grant 51773124) 2019-02-04T15:57:24Z 2019-02-04T15:57:24Z 2018-11 2018-09 2019-01-17T13:46:32Z Article http://purl.org/eprint/type/JournalArticle 2040-3364 2040-3372 http://hdl.handle.net/1721.1/120168 Liao, Fen, Ling-Ying Shi, Li-Chen Cheng, Sangho Lee, Rong Ran, Kevin G. Yager, and Caroline A. Ross. “Self-Assembly of a Silicon-Containing Side-Chain Liquid Crystalline Block Copolymer in Bulk and in Thin Films: Kinetic Pathway of a Cylinder to Sphere Transition.” Nanoscale 11, no. 1 (2019): 285–293. © The Royal Society of Chemistry https://orcid.org/0000-0001-9975-9903 https://orcid.org/0000-0003-4164-1827 https://orcid.org/0000-0003-2262-1249 http://dx.doi.org/10.1039/c8nr07685e Nanoscale Creative Commons Attribution 3.0 unported license https://creativecommons.org/licenses/by/3.0/ application/pdf Royal Society of Chemistry Royal Society of Chemistry (RSC) |
| spellingShingle | Liao, Fen Ran, Rong Yager, Kevin G. Shi, Lingying Cheng, Li-Chen Lee, Sangho Ross, Caroline A Self-assembly of a silicon-containing side-chain liquid crystalline block copolymer in bulk and in thin films: kinetic pathway of a cylinder to sphere transition |
| title | Self-assembly of a silicon-containing side-chain liquid crystalline block copolymer in bulk and in thin films: kinetic pathway of a cylinder to sphere transition |
| title_full | Self-assembly of a silicon-containing side-chain liquid crystalline block copolymer in bulk and in thin films: kinetic pathway of a cylinder to sphere transition |
| title_fullStr | Self-assembly of a silicon-containing side-chain liquid crystalline block copolymer in bulk and in thin films: kinetic pathway of a cylinder to sphere transition |
| title_full_unstemmed | Self-assembly of a silicon-containing side-chain liquid crystalline block copolymer in bulk and in thin films: kinetic pathway of a cylinder to sphere transition |
| title_short | Self-assembly of a silicon-containing side-chain liquid crystalline block copolymer in bulk and in thin films: kinetic pathway of a cylinder to sphere transition |
| title_sort | self assembly of a silicon containing side chain liquid crystalline block copolymer in bulk and in thin films kinetic pathway of a cylinder to sphere transition |
| url | http://hdl.handle.net/1721.1/120168 https://orcid.org/0000-0001-9975-9903 https://orcid.org/0000-0003-4164-1827 https://orcid.org/0000-0003-2262-1249 |
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