共聚物定向自组装三维有序结构的研究

Directed self-assembly of block copolymers offers a novel paradigm for building up three-dimensional (3D) ordered nanostructures towards deep sub-100-nm resolution. Since it is currently difficult to directly visualize the interior of 3D structures in experiments, design rules and ordered mechanisms of 3D ordered nanostructures in templates are still elusive. In this proposal, firstly the thermodynamic and kinetic models for the directed self-assembly of block copolymers in the templates are established, and the General-Purpose Graphics Processing Units are utilized to numerically solve the model equations of polymeric systems in large cell simulations. Secondly, we intend to investigate the directed self-assembly behaviors of block copolymer films in the topographical templates, to capture the effects of design parameters of templates on the 3D ordered structures (morphology, orientation and order degree), and to unveil the ordered mechanisms of 3D structures in the solvent vapor annealing. Then, we present design strategies for creating the 3D non-periodic structures with specific defects at desired locations and layers. The effects of solvent vapor annealing are also examined to guarantee the stability of 3D non-periodic structures in the designed templates. These studies will provide insights into the nature of 3D assembled structures of block copolymers, and furthermore offer promising strategies for constructing the 3D device-oriented elements.

共聚物定向自组装提供了一种构筑三维有序微纳结构的新方法。由于实验上缺乏有效的观测和表征手段，共聚物三维有序结构的形成规律和调控机理尚不清楚。本项目将分别建立共聚物定向自组装的热力学和动力学模型，发展适用于超大格子模拟的并行算法；开展纳米柱引导共聚物定向自组装行为的模拟，掌握模板设计参数对三维结构的形貌、取向和有序程度的影响规律，揭示溶剂蒸气退火过程对三维有序结构的调控机理；在此基础上，通过合理的模板设计和溶剂蒸气退火过程，构筑形貌可控的三维非周期性结构。通过上述研究，为共聚物定向自组装三维结构的构筑提供新的设计思路和理论支持。

共聚物引导自组装是实现纳米结构宏量制备的一种技术，在半导体工业中存在潜在应用。本项目以模板引导的共聚物为研究对象，开展了三维长程有序结构的形成规律、有序结构的动力学调控机理以及非周期性结构的模板设计等研究。取得的重要结果如下：（1）通过理性地设计一类引导模板，引导共聚物或者纳米粒子形成内部结构可调的三维有序纳米结构；（2）建立了局域退火模型，从动力学角度调控自组装结构的有序化过程，实现了长程有序、单一取向的纳米结构；（3）发展了逆向模板设计算法，以非周期性图案为目标结构，设计了包含纳米柱的引导模板，实现了特定的大面积非周期性纳米结构。（4）此外，受聚合反应的启发，阐明了纳米粒子自组装形成一维超结构的“类聚合”动力学。以上理论模拟结果为共聚物引导自组装长程有序化的模板设计和动力学调控提供新思路和理论支持。