Solvothermal vapor annealing at elevated temperature is applied to a thin film from a cylinder‐forming polystyrene‐block‐poly(dimethyl siloxane) (PS‐b‐PDMS) diblock copolymer. At this, the film is swollen in the vapor of n‐heptane (highly selective for PDMS). This vapor is stepwise replaced by the vapor of toluene (weakly selective for PS). The morphologies are investigated using in situ, real‐time grazing‐incidence small‐angle X‐ray scattering (GISAXS). The initial cylindrical morphology is transformed into, among others, the lamellar one. This novel type of experiments allows probing a trajectory in the state diagram of the PS‐b‐PDMS/n‐heptane/toluene mixture. To corroborate the morphologies, they are generated by molecular simulations, and the 2D GISAXS maps are calculated using the distorted‐wave Born approximation. To relate the morphologies to the solvent distribution in the two types of nanodomains, the latter is estimated from the intensities of the Bragg reflections in the 2D GISAXS maps along with the swelling ratio of the film. Comparison with the results from a similar experiment carried out at room temperature results in the same sequence of morphologies; however, at elevated temperature, more well‐ordered structures are obtained. This new approach proves to be efficient to achieve a block copolymer thin film having a desired morphology and orientation.

中文翻译：

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在高温下交换溶剂蒸气过程中用GISAXS原位追踪双嵌段共聚物薄膜的组成和形貌

将高温下的溶剂热蒸汽退火应用于圆柱型聚苯乙烯嵌段-聚（二甲基硅氧烷）（PS- b - PDMS）二嵌段共聚物的薄膜。此时，薄膜在正庚烷蒸汽中膨胀（对PDMS具有高度选择性）。该蒸气逐步被甲苯蒸气替代（对PS的选择性差）。使用原位实时掠入射小角度X射线散射（GISAXS）对形态进行了研究。最初的圆柱形态被转化为片层形态。这种新颖的实验类型可以在PS‐ b ‐ PDMS / n的状态图中探测轨迹庚烷/甲苯混合物。为了证实形态，可以通过分子模拟生成形态，并使用扭曲波Born近似来计算2D GISAXS映射。要将形态与两种类型的纳米域中的溶剂分布相关联，可以根据2D GISAXS图中的布拉格反射强度以及薄膜的溶胀率来估算后者。与在室温下进行的类似实验的结果进行比较，得出的结果是相同的形态顺序；但是，在升高的温度下，可以获得更整齐的结构。事实证明，这种新方法对于获得具有所需形态和取向的嵌段共聚物薄膜是有效的。