Progress in Self⁃assembly and Photo⁃responsiveness of Thin Films of Azobenzene⁃Based Liquid Crystalline Block Copolymers

doi:10.19894/j.issn.1000-0518.210372

Chinese Journal of Applied Chemistry ›› 2021, Vol. 38 ›› Issue (10): 1238-1254.DOI: 10.19894/j.issn.1000-0518.210372

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Progress in Self⁃assembly and Photo⁃responsiveness of Thin Films of Azobenzene⁃Based Liquid Crystalline Block Copolymers

Long-Fei LUO^1‡, Yu-Jie LI^2‡, Zhi-Hao SHEN¹(), Shi-Jun ZHENG², Xing-He FAN¹

¹Beijing National Laboratory for Molecular Sciences，Key Laboratory of Polymer Chemistry and Physics of Ministry of Education，Center for Soft Matter Science and Engineering，College of Chemistry and Molecular Engineering，Peking University，Beijing 100871，China
²College of Materials Science and Engineering，Zhengzhou University，Zhengzhou 450000，China

Received:2021-07-29 Accepted:2021-08-31 Published:2021-10-01 Online:2021-10-15
Contact: Zhi-Hao SHEN
About author:zshen@pku.edu.cn
Supported by:
National Key R&D Program of China(2018YFB0703702);the National Natural Science Foundation of China(51725301)

Abstract

Abstract:

As a type of block copolymers （BCPs） containing an azobenzene-containing liquid crystalline （LC） block， azobenzene-based LC BCPs （LCBCPs）， have attracted the attention of researchers in the fields of nanotechnology， information storage， and photonics， owing to the combination of the microphase separation of BCPs， the ordered LC structures of LC polymers， and the photo-responsiveness of azobenzene mesogens. In this review， the recent research progresses in self-assembly and photo-responsiveness of thin films of azobenzene-based LCBCPs are summarized. The principles of the excluded volume effect and the surface segregation are introduced. In addition， the influences of the excluded volume effect and the surface segregation on the self-assembled structures and the photo-induced orientation of azobenzene-based LCBCP films are also discussed. The light regulation with different light sources， including linearly polarized light， ultraviolet （UV） light and unpolarized light， on the self-assembled structures of azobenzene-based LCBCPs are described. In addition， the functional applications of azobenzene-based LCBCP films are also briefly introduced. Then， the challenges of current research on the self-assembly of thin films of azobenzene-based LCBCPs are discussed. Finally， the future research prospects of azobenzene-based LCBCPs are proposed.

Key words: Azobenzene liquid crystalline polymer, Photo-responsiveness, Block copolymer, Thin-film self-assembly, Excluded volume effect, Surface segregation, Functional application

CLC Number:

O631

Long-Fei LUO, Yu-Jie LI, Zhi-Hao SHEN, Shi-Jun ZHENG, Xing-He FAN. Progress in Self⁃assembly and Photo⁃responsiveness of Thin Films of Azobenzene⁃Based Liquid Crystalline Block Copolymers[J]. Chinese Journal of Applied Chemistry, 2021, 38(10): 1238-1254.

Figures/Tables 13

Fig.1 （a） Schematic diagram of excluded volume between the molecules of rodlike mesogens and solid surface；（b） Schematic representation of the orientation of rod-like CB mesogens on free surface and solid surface［64］

Fig.2 （a） Morphologies of CNA57B14-TFSI films with different thicknesses after thermal annealing and the absorption values at 350 nm before and after thermal annealing （Copyright 2021 American Chemical Society）［65］；（b） Morphologies of A101B22-TFSI films with different thicknesses after solvent vapor annealing and the absorption values at 336 nm before and after solvent vapor annealing （Copyright 2020 American Chemical Society）［20］

Fig.3 （a） Schematic diagram of the orientation of azobenzene molecules induced by linearly polarized light （LPL）［57］；（b） Direction for nonefficient photoreaction in an Az unit［61］；（c） Orientation of LC mesogens in an IMDS of a BCP containing an LCP［61］

Fig.4 Schematic diagrams of the arrangement of azobenzene mesogens in homopolymer PAz film and block copolymer PBMA-b-PAz film （a： homopolymer PAz； b： block copolymer PBMA-b-PAz）［61］

Fig.5 （a） Chemical structures of homopolymer PAz and block copolymers PBMA-b-PAz and PS-b-PAz； Schematic diagrams of in-plane orientation induced by surface segregation of PBMA-b-PAz and photo-induced in-plane uniaxial alignment of azobenzene mesogens in PAz film （b） and PS-b-PAz film （c）［70］

Fig.6 （a） Schematic diagram of alignment of azobenzene mesogens and microphase-separated structures in the irradiated and unirradiated areas of the azobenzene LCBCP films［36］；（b） Schematic diagram of the arrangement of PEO cylinders in regions of different thicknesses in the surface-relief structures produced by two coherent LPL of the azobenzene LCBCP films［79］；（c） Absorption values of azobenzene LCBCP films with different thicknesses before and after being aligned with LPL and the morphologies of LPL aligned films［65］

Fig.7 （a） Schematic diagram of the arrangement of various hierarchical structures in the process of the rearrangement of the oriented structure induced by LPL［38］；（b） Chemical structures of diblock copolymers and triblock copolymers and the rearrangement of the oriented structures induced by LPL［40］

Fig.8 Morphologies of the thermally annealed PEO-b-PAzPy films before and after being doped with 1，2-DITFB， and morphologies of PEO-b-PAzPy films doped with 1，2-DITFB after photo-alignment by LPL［81］

Fig.9 Morphologies of PEO-b-PM11Az film before and after UV light irradiation and schematic diagram of the orientation transformation of PEO nanocylinders induced by the photo-induced phase transition［39］

Fig.10 Morphologies of CNA57B14-TFSI thin films with different thicknesses after thermal annealing and unpolarized light （UPL） orientation［65］

Fig.11 Schematic diagram of the morphologies of PDMS65-b-PAz35 thin films after thermal annealing and UPL orientation［82］

Fig.12 Chemical structure of P40A37 and schematic diagram of the structures of the holographic grating recorded on P40A37 thin film before and after annealing［12］

Fig.13 （a） Schematic diagrams of preparing patterned CaCO3 nanoparticles using the microphase-separated structures of azobenzene-based LCBCP before and after light regulation as the templates［13］；（b） Anisotropic ion-conducting membrane prepared with azobenzene-based LCBCP as a nanotemplate ［28］

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Progress in Self⁃assembly and Photo⁃responsiveness of Thin Films of Azobenzene⁃Based Liquid Crystalline Block Copolymers

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