浸涂过程中超分子含氮嵌段共聚物薄膜的光控制：纳米图案化涂料。,ACS Applied Energy Materials

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浸涂过程中超分子含氮嵌段共聚物薄膜的光控制：纳米图案化涂料。
ACS Applied Energy Materials ( IF 5.4 ) Pub Date : 2019-05-07 00:00:00 , DOI: 10.1021/acsanm.9b00496
Jaana Vapaavuori ₁ , Josué Grosrenaud ₁ , Antti Siiskonen ₂ , Arri Priimagi ₂ , Christian Pellerin ₁ , C. Geraldine Bazuin ₁

Affiliation

浸涂使得纳米结构嵌段共聚物（BCP）薄膜可以快速，简便的一步法生产。它还可以与外部控件（例如照明）耦合。本文中，我们介绍了一些设计原理，这些设计原理可以对纳米结构的BCP薄膜的纳米结构表面图案和厚度进行光控。这是通过使用聚苯乙烯-聚（4-乙烯基吡啶）（PS-P4VP）BCP和两个具有不同光化学特性且氢键与P4VP嵌段键合的羟基官能化小分子（SM）偶氮衍生物完成的。我们展示了膜制备概念如何通过光敏SM的化学结构，浸涂溶液中SM的相对量以及溶剂的选择来提供可调性。已经发现，当使用THF时，通过照射增加了膜的膜厚度和SM吸收，但是当使用甲苯作为溶剂时，膜厚度和SM吸收没有改变，这归因于挥发性溶剂可观察到的光学加热效果。表面图案的光控制是P4VP + SM相有效体积分数发生光诱导变化的结果，P4VP + SM相的有效体积分数随光体积的增加而增加。顺式异构体，更高的SM吸收（使用THF）以及更多的反式-顺式-反式循环，从而缩短了顺式寿命。由于更灵活的SM，较低的BCP分子量以及非胶束或较软的胶束溶液，较高的分子迁移率也可以增加光诱导变化的程度。

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Photocontrol of Supramolecular Azo-Containing Block Copolymer Thin Films during Dip-Coating: Toward Nanoscale Patterned Coatings

Dip-coating allows nanostructured block copolymer (BCP) thin film fabrication in a fast and facile one-step process. It can also be coupled with external controls, such as illumination. Herein, we expose several design principles that enable photocontrol of the nanostructured surface pattern and thickness of supramolecular BCP thin films. This is done using a polystyrene–poly(4-vinylpyridine) (PS-P4VP) BCP and two hydroxy-functionalized small-molecule (SM) azo derivatives that have different photochemical characteristics and that hydrogen bond to the P4VP block. We show how the film preparation concept provides tunability through the chemical structure of the photoactive SM, the relative amount of SM in the dip-coating solution, and the choice of solvent. It was found that the film thickness and SM uptake in the films are increased by illumination when THF is used but are unchanged when toluene is used as solvent, which is attributed to an optical heating effect observable with volatile solvents. The photocontrol of surface patterns is a result of photoinduced changes in the effective volume fraction of the P4VP+SM phase, which is increased by a greater volume of cis isomers, by higher SM uptake (using THF), and by more trans–cis–trans cycling for systems with shorter cis lifetime. The extent of photoinduced change can also be increased by higher molecular mobility due to more flexible SMs, lower BCP molecular weight, and nonmicellar or softer micellar solutions.

更新日期：2019-05-07

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