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Title: Self-Assembly and Post-Fabrication Functionalization of Microphase Separated Thin Films of a Reactive Azlactone-Containing Block Copolymer

Abstract

We report on the thin film self-assembly and post-fabrication functionalization of cylinder-forming poly(styrene-block-2-vinyl-4,4-dimethylazlactone) (PS-b-PVDMA) block copolymers (BCPs). Thermal annealing of an asymmetric BCP composition, to drive microphase separation in thin films, results in high defect densities and poor long-range order. Using FTIR spectroscopy and ellipsometry, we demonstrate that thermal annealing results in reactions between the azlactone groups and the underlying substrate leading to BCP “pinning”. Further, we demonstrate that solvent annealing circumvents these issues and drives high fidelity microphase separation of the BCP in thin films. The solvent annealing approach also enables control over domain orientation; we show that parallel and perpendicularly oriented cylinders with diameters of 11.7 ± 1.2 nm and a center-to-center distance of 25.2 ± 2.6 nm can be obtained using a BCP with M n = 29.5 kDa and f S = 0.75. The PVDMA segments in these self-assembled thin films remain available for reaction with primary amine-functionalized nucleophiles. X-ray photoelectron spectroscopy (XPS) depth-profiling reveals that reactions between azlactone groups and incoming amines occur primarily in the top few nanometers of the reactive domains. Finally, we demonstrate that the azlactone groups in both parallel and perpendicularly oriented cylindrical thin films can selectively incorporate trimethylaluminum vapor, whichmore » can be subsequently converted into Al 2O 3 nanowires and nanodots with dimensions of 16 and 12 nm, respectively.« less

Authors:
 [1];  [1];  [1];  [1];  [1];  [2];  [1];  [1]
  1. Univ. of Wisconsin, Madison, WI (United States)
  2. Univ. of Minnesota, Minneapolis, MN (United States); Univ. of Wisconsin, Madison, WI (United States)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Sponsoring Org.:
National Science Foundation (NSF); Natural Sciences and Engineering Research Council of Canada (NSERC)
OSTI Identifier:
1351371
Grant/Contract Number:  
1462771; AC02-06CH11357
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Macromolecules
Additional Journal Information:
Journal Volume: 49; Journal Issue: 21; Journal ID: ISSN 0024-9297
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
ENGLISH
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Morphology; Self organization; Thin films; Solvents; Thermal annealing

Citation Formats

Choi, Jonathan W., Carter, Matthew C. D., Wei, Wei, Kanimozi, Catherine, Speetjens, Frank W., Mahanthappa, Mahesh K., Lynn, David M., and Gopalan, Padma. Self-Assembly and Post-Fabrication Functionalization of Microphase Separated Thin Films of a Reactive Azlactone-Containing Block Copolymer. United States: N. p., 2016. Web. doi:10.1021/acs.macromol.6b01734.
Choi, Jonathan W., Carter, Matthew C. D., Wei, Wei, Kanimozi, Catherine, Speetjens, Frank W., Mahanthappa, Mahesh K., Lynn, David M., & Gopalan, Padma. Self-Assembly and Post-Fabrication Functionalization of Microphase Separated Thin Films of a Reactive Azlactone-Containing Block Copolymer. United States. https://doi.org/10.1021/acs.macromol.6b01734
Choi, Jonathan W., Carter, Matthew C. D., Wei, Wei, Kanimozi, Catherine, Speetjens, Frank W., Mahanthappa, Mahesh K., Lynn, David M., and Gopalan, Padma. Wed . "Self-Assembly and Post-Fabrication Functionalization of Microphase Separated Thin Films of a Reactive Azlactone-Containing Block Copolymer". United States. https://doi.org/10.1021/acs.macromol.6b01734. https://www.osti.gov/servlets/purl/1351371.
@article{osti_1351371,
title = {Self-Assembly and Post-Fabrication Functionalization of Microphase Separated Thin Films of a Reactive Azlactone-Containing Block Copolymer},
author = {Choi, Jonathan W. and Carter, Matthew C. D. and Wei, Wei and Kanimozi, Catherine and Speetjens, Frank W. and Mahanthappa, Mahesh K. and Lynn, David M. and Gopalan, Padma},
abstractNote = {We report on the thin film self-assembly and post-fabrication functionalization of cylinder-forming poly(styrene-block-2-vinyl-4,4-dimethylazlactone) (PS-b-PVDMA) block copolymers (BCPs). Thermal annealing of an asymmetric BCP composition, to drive microphase separation in thin films, results in high defect densities and poor long-range order. Using FTIR spectroscopy and ellipsometry, we demonstrate that thermal annealing results in reactions between the azlactone groups and the underlying substrate leading to BCP “pinning”. Further, we demonstrate that solvent annealing circumvents these issues and drives high fidelity microphase separation of the BCP in thin films. The solvent annealing approach also enables control over domain orientation; we show that parallel and perpendicularly oriented cylinders with diameters of 11.7 ± 1.2 nm and a center-to-center distance of 25.2 ± 2.6 nm can be obtained using a BCP with Mn = 29.5 kDa and fS = 0.75. The PVDMA segments in these self-assembled thin films remain available for reaction with primary amine-functionalized nucleophiles. X-ray photoelectron spectroscopy (XPS) depth-profiling reveals that reactions between azlactone groups and incoming amines occur primarily in the top few nanometers of the reactive domains. Finally, we demonstrate that the azlactone groups in both parallel and perpendicularly oriented cylindrical thin films can selectively incorporate trimethylaluminum vapor, which can be subsequently converted into Al2O3 nanowires and nanodots with dimensions of 16 and 12 nm, respectively.},
doi = {10.1021/acs.macromol.6b01734},
url = {https://www.osti.gov/biblio/1351371}, journal = {Macromolecules},
issn = {0024-9297},
number = 21,
volume = 49,
place = {United States},
year = {2016},
month = {10}
}

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Fit-for-purpose block polymer membranes molecularly engineered for water treatment
journal, April 2018