Insights into the influence of solvent polarity on the crystallization of poly(ethylene oxide) spin-coated thin films via in situ grazing incidence wide-angle X-ray scattering


Controlling polymer thin-film morphology and crystallinity is crucial for a wide range of applications, particularly in thin-film organic electronic devices. In this work, the crystallization behavior of a model polymer, poly(ethylene oxide) (PEO), during spin-coating is studied. PEO films were spun-cast from solvents possessing different polarities (chloroform, THF, and methanol) and probed via in situ grazing incidence wide-angle X-ray scattering. The crystallization behavior was found to follow the solvent polarity order (where chloroform < THF < methanol) rather than the solubility order (where THF > chloroform > methanol). When spun-cast from nonpolar chloroform, crystallization largely followed Avrami kinetics, resulting in the formation of morphologies comprising large spherulites. PEO solutions cast from more polar solvents (THF and methanol) do not form well-defined highly crystalline morphologies and are largely amorphous with the presence of small crystalline regions. The difference in morphological development of PEO spun-cast from polar solvents is attributed to clustering phenomena that inhibit polymer crystallization. This work highlights the importance of considering individual components of polymer solubility, rather than simple total solubility, when designing processing routes for the generation of morphologies with optimum crystallinities or morphologies.

Publication DOI:
Divisions: College of Engineering & Physical Sciences > School of Infrastructure and Sustainable Engineering > Chemical Engineering & Applied Chemistry
College of Engineering & Physical Sciences > Aston Institute of Materials Research (AIMR)
Additional Information: This document is the Accepted Manuscript version of a Published Work that appeared in final form in Macromolecules, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see
Uncontrolled Keywords: Organic Chemistry,Materials Chemistry,Polymers and Plastics,Inorganic Chemistry
Publication ISSN: 1520-5835
Last Modified: 15 Jul 2024 07:21
Date Deposited: 19 Aug 2019 10:08
Full Text Link: http://eprints. ...
Related URLs: http://www.scop ... tnerID=8YFLogxK (Scopus URL)
http://pubs.acs ... acromol.6b00312 (Publisher URL)
PURE Output Type: Article
Published Date: 2016-06-28
Published Online Date: 2016-06-20
Accepted Date: 2016-05-20
Authors: Toolan, Daniel T.W.
Isakova, Anna
Hodgkinson, Richard
Reeves-McLaren, Nik
Hammond, Oliver S.
Edler, Karen J.
Briscoe, Wuge H.
Arnold, Thomas
Gough, Tim
Topham, Paul D. (ORCID Profile 0000-0003-4152-6976)
Howse, Jonathan R.



Version: Accepted Version

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