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Solvent Vapor Annealing of a Diblock Copolymer Thin Film with a Nonselective and a Selective Solvent: Importance of Pathway for the Morphological Changes.
Macromolecular Rapid Communications ( IF 4.2 ) Pub Date : 2020-06-16 , DOI: 10.1002/marc.202000150
Florian A Jung 1 , Anatoly V Berezkin 1 , Tim B Tejsner 2 , Dorthe Posselt 2 , Detlef-M Smilgies 3 , Christine M Papadakis 1
Affiliation  

Diblock copolymer thin films of polystyrene‐block‐poly(dimethyl siloxane) (PS‐b‐PDMS) featuring PDMS cylinders in a PS matrix are investigated during solvent vapor annealing with mixtures of n‐heptane (which is strongly selective for PDMS) and toluene (which is close to nonselective for both blocks). Swelling in the vapor of one of the pure solvents and exchanging it stepwise by the vapor of the other solvent is compared to swelling in a given binary solvent vapor mixture for a prolonged time. The resulting structural changes, such as ordering of the cylinders on a hexagonal lattice and their transition into lamellae, are followed using in situ, real‐time grazing‐incidence small‐angle X‐ray scattering (GISAXS). In three runs, the sequence of solvent vapor swelling and vapor exchange is varied. Compiling the resulting morphologies in a diagram of states in dependence on the solvent content in the film and in the minority nanodomains allows insight into the role of the glass transition of the PS matrix for the ordering processes and their time scales. Based on these findings, a protocol is suggested to efficiently obtain an order‐to‐order transition from the cylindrical morphology with random domain orientation to the oriented lamellar state.

中文翻译:

具有非选择性和选择性溶剂的双嵌段共聚物薄膜的溶剂蒸汽退火:形态变化途径的重要性。

在溶剂蒸汽退火过程中,研究了以n为混合物的聚苯乙烯嵌段聚二甲基硅氧烷(PS- b -PDMS )的二嵌段共聚物薄膜在PS基体中的PDMS圆柱体庚烷(对PDMS的选择性强)和甲苯(对两个嵌段的选择性接近)。将一种纯溶剂的蒸气溶胀并与另一种溶剂的蒸气逐步交换进行比较,可以与在给定的二元溶剂蒸气混合物中长时间溶胀相比较。由此产生的结构变化,例如圆柱体在六边形晶格上的排序以及它们向薄片的过渡,都使用原位实时掠入射小角度X射线散射(GISAXS)进行跟踪。在三个运行中,溶剂蒸气溶胀和蒸气交换的顺序有所不同。根据薄膜中和少数纳米域中的溶剂含量,以状态图的形式编译所得的形态,可以洞悉PS基质的玻璃化转变对于有序过程及其时标的作用。基于这些发现,提出了一种协议,以有效地获得从具有随机域取向的圆柱形态到取向层状态的从订单到订单的过渡。
更新日期:2020-07-20
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