嵌段高分子自组装形成纳米尺度的有序结构，其相区尺寸的进一步减小与高分子在有机光电材料、纳米材料及先进光刻技术领域的应用紧密相关。为此，通过在嵌段高分子中引入链刚性以及氢键作用，以期制备有序的更小尺寸纳米结构。本项目拟设计含有氢键的复杂构型刚-柔嵌段高分子体系，通过自洽场理论计算预测其自组装形成各种镶嵌结构的机理，深入考察链刚性、氢键作用及刚性链段之间的取向相互作用对相结构的影响。同时结合弦方法追踪无序-有序、有序-有序及不同亚稳态之间的转变路径、成核过程，理解链构象与凝聚态结构之间的关联机制，预测刚性高分子体系与材料的功能性及物理性能之间的关系。这些工作有助于为具有精密介观相结构的高性能功能材料的分子设计及其动力学路径设计提供理论依据。

Block copolymers can self-assemble into nanoscale ordered structures. The domain size is strongly related to the performance of organic optoelectronics, nanomaterials and next-generation lithography. This proposal aims to develop the strategy to decrease the domain size of nanostructures by introducing chain rigidity and hydrogen-bond interaction to block copolymers with complex chain architecture. On the basis of self-consistent field theory (SCFT), we plan to design the X-shaped rod-coil molecules with hydrogen bonding groups, to analyze its self-assembled behavior into Archimedean tiling patterns, influenced by chain rigidity, hydrogen-bond and orientation interactions. Furthermore, by combining with string method, we will investigate the transition path between phase structures, the emergence of various metastable states and their dependence on the pathway as well as the nucleation process, including the shape and orientation structure of the critical nucleus and the nucleation barrier. We aim to understand the relationship between the condensed ordered structure and the molecular properties, as well as the physical properties of these ordered structures. In this way, we expect to realize the design and regulation of the kinetic pathways to the ordered structures with expected high performance and functionality.