Zhao Wenfeng, Li Weihua
State Key Laboratory of Molecular Engineering of Polymers, Key Laboratory of Computational Physical Sciences, Department of Macromolecular Science, Fudan University, Shanghai 200433, China.
Phys Chem Chem Phys. 2019 Aug 28;21(34):18525-18532. doi: 10.1039/c9cp02667c.
The surface affinity is a critical factor for controlling the formation of monolayer nanostructures in block copolymer thin films. In general, strong surface affinity tends to induce the formation of domains with low spontaneous curvature. Abiding by this principle, we propose a facile chemoepitaxial scheme for producing large-scale ordered hybrid patterns by the directed self-assembly of diblock copolymers. The guiding chemical pattern is designed as periodic stripes with alternately changing surface affinities. As a consequence, two different geometries of domains are formed on the stripes with different affinities. The self-assembly process of block copolymers guided by the stripe patterns is investigated using cell dynamics simulations based on time-dependent Ginzburg-Landau theory, and the kinetic stability diagram is estimated. Hybrid patterns are successfully achieved with both cylinder-forming and sphere-forming diblock copolymers. In the cylinder-forming system, the major hybrid pattern exhibiting a considerable stability window is composed of parallel cylinders and perforated lamellae, while it is composed of monolayer spheres and parallel cylinders in the other system. Encouragingly, the chemoepitaxial method is valid till the period of the guiding pattern is a large multiple of the domain spacing. The chemoepitaxial scheme demonstrated in this work serves as a nice supplement to the graphoepitaxial one proposed in our previous work.
表面亲和力是控制嵌段共聚物薄膜中单层纳米结构形成的关键因素。一般来说,强表面亲和力倾向于诱导形成具有低自发曲率的畴。遵循这一原理,我们提出了一种简便的化学外延方案,通过二嵌段共聚物的定向自组装来制备大规模有序的混合图案。引导化学图案被设计为具有交替变化表面亲和力的周期性条纹。结果,在具有不同亲和力的条纹上形成了两种不同几何形状的畴。基于时间相关的金兹堡 - 朗道理论,使用元胞动力学模拟研究了由条纹图案引导的嵌段共聚物的自组装过程,并估计了动力学稳定性图。使用形成圆柱和形成球体的二嵌段共聚物都成功实现了混合图案。在形成圆柱的体系中,表现出相当大稳定性窗口的主要混合图案由平行圆柱和穿孔薄片组成,而在另一个体系中它由单层球体和平行圆柱组成。令人鼓舞的是,化学外延方法在引导图案的周期是畴间距的很大倍数时仍然有效。这项工作中展示的化学外延方案是我们之前工作中提出的图形外延方案的很好补充。