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Quantitative analysis of stereoscopic molecular orientations in thermally reactive and heterogeneous noncrystalline thin films via variable-temperature infrared pMAIRS and GI-XRD

Polymer Journal volume 53, pages 603–617 (2021)Cite this article

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Abstract

The quantitative estimation of stereoscopic molecular orientations in semicrystalline polymer thin films with characteristic heterogeneous structures is essential for the development of advanced film materials. Grazing-incidence X-ray diffraction (GI-XRD) is a powerful technique used to evaluate the orientational order of crystalline lattices; however, it provides the orientational order of only ordered regions (crystal and glassy liquid crystal regions). In contrast, infrared (IR) p-polarized multiple-angle incidence resolution spectrometry (pMAIRS) can provide the averaged orientational order of overall regions in a film regardless of sample crystallinity. This paper combines variable-temperature (VT) pMAIRS, static GI-XRD and spectroscopic ellipsometry and reports general insight into the molecular orientation mechanism occurring in polymer films revealed through the precise analysis of the structural evolution of linear poly(amic n-alkyl ester), PAE, with different lengths of n-alkyl chains during thermal curing, which involves solvent evaporation and dehydration imidization reactions to form the corresponding polyimide (PI). This combined method clarified that the PAE and PI thin films had a heterogeneous structure consisting of a glassy liquid-crystalline (ordered) region and a nonoriented amorphous region. Furthermore, imidization proceeded faster in the amorphous region than in the ordered (oriented) region. In addition, anomalies of refractive index and birefringence were found by comparing pMAIRS and spectroscopic ellipsometry, although the effect of the side chain length on the molecular orientation of PI was insignificant. The anomalies indicate that an isotropic void structures were generated by the elimination reaction of the side chains and that the volume fraction of voids increased with increasing side chain length. These results demonstrated that the combination of VT-pMAIRS and GI-XRD is a very powerful tool for the in situ structural analyses of noncrystalline (disordered crystal, glassy liquid crystal, and oriented amorphous) thin-film materials ongoing chemical reactions in their components and is inherently applicable to all kinds of interesting polymeric thin-film materials.

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Acknowledgements

This work was partly supported by Grants-in-Aid for Scientific Research, Japan Society for the Promotion of Science (18K05213). The synchrotron radiation experiments were performed at BL-6A and BL-10C of the High Energy Accelerator Research Organization with the approval of the Photon Factory Program Advisory Committee (Proposal Nos. 2019G673, 2018G651, and 2017G693). The authors are grateful to Dr. Saiko Aoki, professor of Tokyo Institute of Technology, for her kind support with the spectroscopic ellipsometry of the PI films. We also acknowledge Dr. Tomoya Higashihara, professor of Yamagata University, for his fruitful discussions and salient advice on the imidization of the meta- and para-isomers of poly(amic acid).

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  1. Department of Chemical Science and Engineering, School of Materials and Chemical Technology, Tokyo Institute of Technology, E4-5, 2-12-1 Ookayama, Meguro-ku, Tokyo, 152-8552, Japan

    Ryohei Ishige, Kazuyuki Tanaka & Shinji Ando

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  1. Ryohei Ishige
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Quantitative analysis of stereoscopic molecular orientations in thermally reactive and heterogeneous noncrystalline thin films via variable-temperature infrared pMAIRS and GI-XRD

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Ishige, R., Tanaka, K. & Ando, S. Quantitative analysis of stereoscopic molecular orientations in thermally reactive and heterogeneous noncrystalline thin films via variable-temperature infrared pMAIRS and GI-XRD. Polym J 53, 603–617 (2021). https://doi.org/10.1038/s41428-020-00458-8

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