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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

Abstract

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. In conclusion, the transient morphologies from the HEX tomore » BCC structure in thin films were captured by scanning electron microscopy and atomic force microscopy, and the transition pathway was described.« less

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [3]; ORCiD logo [1]; ORCiD logo [4]; ORCiD logo [3]
  1. Sichuan Univ., Chengdu (China)
  2. Sichuan Univ., Chengdu (China); Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
  3. Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
  4. Brookhaven National Lab. (BNL), Upton, NY (United States)
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1491134
Report Number(s):
BNL-210885-2019-JAAM
Journal ID: ISSN 2040-3364; NANOHL
Grant/Contract Number:  
SC0012704
Resource Type:
Accepted Manuscript
Journal Name:
Nanoscale
Additional Journal Information:
Journal Volume: 11; Journal Issue: 1; Journal ID: ISSN 2040-3364
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
77 NANOSCIENCE AND NANOTECHNOLOGY; block copolymer

Citation Formats

Liao, Fen, Shi, Ling -Ying, Cheng, Li -Chen, Lee, Sangho, Ran, Rong, Yager, Kevin G., and 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. United States: N. p., 2018. Web. doi:10.1039/C8NR07685E.
Liao, Fen, Shi, Ling -Ying, Cheng, Li -Chen, Lee, Sangho, Ran, Rong, Yager, Kevin G., & 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. United States. doi:10.1039/C8NR07685E.
Liao, Fen, Shi, Ling -Ying, Cheng, Li -Chen, Lee, Sangho, Ran, Rong, Yager, Kevin G., and Ross, Caroline A. Mon . "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". United States. doi:10.1039/C8NR07685E. https://www.osti.gov/servlets/purl/1491134.
@article{osti_1491134,
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},
author = {Liao, Fen and Shi, Ling -Ying and Cheng, Li -Chen and Lee, Sangho and Ran, Rong and Yager, Kevin G. and Ross, Caroline A.},
abstractNote = {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. In conclusion, 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.},
doi = {10.1039/C8NR07685E},
journal = {Nanoscale},
number = 1,
volume = 11,
place = {United States},
year = {2018},
month = {11}
}

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Figures / Tables:

Fig. 1 Fig. 1 : The chemical structure of PDMS-b-P(4CNB11C)MA side chain LC block copolymer (a), and the DSC curves of this BCP in the second heating scan (red) and in the second cooling scan (black) with a scanning rate of 10 °C/min.

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    Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.