Probing the Surface Curie Temperature of Ferroelectric P(VDF-ran-TrFE) Copolymers by Argon Gas Cluster Ion Scattering

Chundak, Mykhailo;Poleunis, Claude;Delmez, Vincent;Jonas, Alain;Delcorte, Arnaud
(2022) The Journal of Physical Chemistry C — Vol. 126, n° 2, p. 1125-1131 (2022)

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This article proposes a new approach to study the temperature dependence of the structural and mechanical changes occurring at the Curie point at the surface of ferroelectric polymers. For this purpose, we used a secondary ion mass spectrometer equipped with a gas cluster ion beam. The intensities of the backscattered Arn+ clusters were measured upon 10 keV Ar3000+ bombardment of a series of P(VDF-ran-TrFE) copolymer thin films and used to calculate the breaking ratios Ar2+/(Ar2+ + Ar3+)and Ar2+/(Ar2+ + Ar4+). The temperature dependences of the breaking ratios prove to be sensitive to the changes in the structural and physical properties of the polymer surfaces. The experiments reveal the transition temperature TT (related to the bulk glass-transition temperature Tg) and the Curie temperature (Tc), indicating the ferroelectric to paraelectric transition in P(VDF-ran-TrFE) polymers. The results agree well with our DSC measurements and with mechanical measurements from the literature, showing that the surface Curie transition remains close to the bulk value in these copolymers. The developed approach was named gas cluster ion scattering spectrometry (GCISS), in reference to the well-known technique of ion scattering spectrometry. GCISS proves to be a versatile approach for the local measurement of structural changes occurring in polymer thin films.
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Chundak, M., Poleunis, C., Delmez, V., Jonas, A., & Delcorte, A. (2022). Probing the Surface Curie Temperature of Ferroelectric P(VDF-ran-TrFE) Copolymers by Argon Gas Cluster Ion Scattering. The Journal of Physical Chemistry C, 126(2), 1125-1131. https://doi.org/10.1021/acs.jpcc.1c06564 (Original work published 2022)