Strongly Phase-Segregating Block Copolymers with Sub-20 nm Features

Kristian Kempe; Kato L Killops; Justin E Poelma; Hyunjung Jung; Joona Bang; Richard Hoogenboom; Helen Tran; Craig J Hawker; Ulrich S Schubert; Luis M Campos

doi:10.1021/mz400309d

Strongly Phase-Segregating Block Copolymers with Sub-20 nm Features

ACS Macro Lett. 2013 Aug 20;2(8):677-682. doi: 10.1021/mz400309d. Epub 2013 Jul 19.

Authors

Kristian Kempe^{1

2

3}, Kato L Killops⁴, Justin E Poelma³, Hyunjung Jung⁵, Joona Bang⁵, Richard Hoogenboom⁶, Helen Tran⁷, Craig J Hawker^{3

8}, Ulrich S Schubert^{1

2

9}, Luis M Campos⁷

Affiliations

¹ Laboratory of Organic and Macromolecular Chemistry (IOMC), Friedrich-Schiller-Universität Jena, Humboldtstr. 10, 07743 Jena, Germany.
² Jena Center for Soft Matter (JCSM), Friedrich-Schiller-Universität Jena, Philosophenweg 7, 07743 Jena, Germany.
³ Materials Research Laboratory, Materials Department, and Department of Chemistry & Biochemistry, University of California, Santa Barbara, California 93016, United States.
⁴ Edgewood Chemical Biological Center, Aberdeen Proving Ground, Maryland 21010, United States.
⁵ Department of Chemical and Biological Engineering, Korea University, 136-713 Seoul, Republic of Korea.
⁶ Supramolecular Chemistry Group, Department of Organic Chemistry, Ghent University, Krijgslaan 281 S4, B-9000 Ghent, Belgium.
⁷ Department of Chemistry, Columbia University, New York, New York 10027, United States.
⁸ Visiting Chair Professor at King Fahd University of Petroleum and Minerals, Dhahran, Saudi Arabia 31261.
⁹ Dutch Polymer Institute (DPI), John F. Kennedylaan 2, 5612 AB Eindhoven, The Netherlands.

PMID: 35606952
DOI: 10.1021/mz400309d

Abstract

The modular synthesis and lithographic potential of diblock copolymers based on polystyrene-block-poly(2-ethyl-2-oxazoline) (PS-b-PEtOx) are highlighted herein. Controlled radical and living cationic polymerization techniques were utilized to synthesize hydrophobic PS and hydrophilic PEtOx building block of varying molar mass. Subsequently, "click" chemistry was used to couple the blocks and obtain a family of PS-b-PEtOx polymers. The influence of molar mass, composition, and thin-film thickness on the microphase-segregated morphology and orientation were investigated with atomic force microscopy (AFM) and grazing incidence small-angle X-ray scattering (GISAXS). Dense hexagonal arrays of cylindrical nanodomains normal to the substrate, having a periodicity of less than 20 nm were obtained.