随着现代电子器件的微型化与可穿戴化发展，聚（偏氟乙烯-三氟乙烯）（P(VDF-TrFE)）作为一类具有本征柔性与优异铁电性的功能材料正在多个领域崭露头角。取向晶体的极化组装与电场响应行为对高结晶性P(VDF-TrFE)的性能分析与优化具有重要意义。由于缺乏简易高效的取向方法，P(VDF-TrFE)中极化分布与响应规律的深入分析与系统认知受限，阻碍了其铁电理论发展与性能优化。本论文围绕含有片状晶粒的P(VDF-TrFE)薄膜，采用自组装法与尺寸限域法分别制备了沿(110)/(020)取向的竖立片晶与沿(001)取向的平躺片晶薄膜，对P(VDF-TrFE)薄膜铁电畴生长动力学过程、铁电自发极化组装行为等基本问题进行了深入研究。 为实现P(VDF-TrFE)薄膜中的竖立片晶取向，发展了一种自组装制备法。结构与电学表征验证了该方法对竖立片晶的高效诱导作用。使用压电力显微镜（PFM）技术激发了微区极化翻转，利用蠕变模型拟合了单片晶内铁电畴壁的迁移。结合第一性原理计算，提出翻转伴生的弹性形变导致了畴壁迁移的蠕变性。 在竖立片晶薄膜中，通过形貌与化学信息分布确认了晶相与非晶相竖立排列的周期性结构。利用PFM，探究了两相自发极化在界面处的耦合，发现非晶相内荷电缺陷可钉扎界面处的荷电畴壁。竖立片晶薄膜中畴壁钉扎与电畴消退的各向异性具有良好方向匹配性，使得薄膜内的铁电畴具有更高的稳定性。该类铁电畴的热耐受温度高达90°C，在30°C与80°C之间12次循环后依然保持稳定。 为实现P(VDF-TrFE)薄膜中的平躺片晶取向，发展了一种尺寸限域制备方法。利用PFM观察了平躺片晶内新奇的极性涡旋拓扑。P(VDF-TrFE)的居里相变在平躺片晶内引入7.3%的双轴拉伸应变，降低了各极化态之间的能量差异，因而诱导了极性涡旋拓扑的产生。在太赫兹偏振光照射下观测了平躺片晶中光学吸收的空间周期性分布，提供了新颖的空间光调制方法。 在平躺片晶中揭示了P(VDF-TrFE)沿c轴方向的铁电性，在多个成分中确认了c轴铁电性的普遍存在。应变调制与成分调制的平躺片晶展现极性拓扑涡旋序与c轴介电弛豫性的共存。利用畴宽-膜厚-畴曲率关联确认了弛豫成分片晶内的超低畴壁能与涡旋序对局部铁电序的稳定化作用，揭示了弛豫铁电聚合物在类泥水状极性结构中展现的涡旋极性微区结构。

Poly(vinylidene fluoride-trifluoroethylene) (P(VDF-TrFE)) has attached extensive research interests because of its flexibility and ferroelectricity, being one of the most competitive candidates for flexible ferroelectric component in wearable and miniaturized electronic devices. Studies of P(VDF-TrFE) with oriented crystallites on the assembly of polarization and its responses to external field should provide insights for understanding and optimizing the ferroelectric behaviors of the crystallizable P(VDF-TrFE). However, due to the lack of methods that could simply and effectively orient the lamellar crystallites in P(VDF-TrFE), analysis and understanding on the assembly and responses of polarization are limited, which hinders the development of theories and optimization of performance in ferroelectric P(VDF-TrFE). Herein, this thesis introduces a self-assembly method and a dimension-limiting method that could respectively fabricate edge-on and face-on lamellae in P(VDF-TrFE) thin films. Observations, analyses and controls on the assembling and responsive behaviors of ferroelectric polarization are conducted within these oriented P(VDF-TrFE) thin films, and are discussed in this thesis. In order to obtain P(VDF-TrFE) thin films with edge-on lamellae, a self-assembly method was applied. Structural and electrical characterization confirmed the effective orientation of edge-on lamellae. After we stimulating microscopic polarization reversal using piezo-responsive force microscopy (PFM), the domain wall motion within a single lamella was analyzed by using creep model fitting. Combining first-principle calculations, the creep motion is proposed to result from the elastic deformation during ferroelectric switching. In P(VDF-TrFE) thin films with edge-on lamellae, morphology and local chemical analyses further confirmed the periodic arrangement of crystal and amorphous phase. By using PFM, the coupling of spontaneous polarization in the two phases at their interface was investigated, and the pinning of charged domain wall at the interface by charged defects in amorphous phase was revealed. The anisotropy of domain wall pinning matches the anisotropy of domain retention in edge-on lamellae, which further stabilizes the reversed ferroelectric domains. The reversed domains exhibited thermal endurance up to 90°C, and could be retained after 12 cycles between 30°C and 80°C. In order to obtain P(VDF-TrFE) thin films with face-on lamellae, a dimension-limiting method was applied. Emergent toroidal polar topology was observed in the face-on lamellae using PFM. The Curie transition of P(VDF-TrFE) introduce a biaxial strain of 7.3% in tensile style onto the face-on lamellae, which decreases the free energy difference among all polarization states and induces the toroidal polar topology. Spatially periodical absorption of tera-hertz wave was observed in thin films with face-on lamellae, providing a novel approach for spatial light modulation. In P(VDF-TrFE) thin films with face-on lamellae, ferroelectricity along c-axis was revealed, with its existence confirmed in lamellae of multiple composition. Modulations on both strain and composition could induce the coexistence of toroidal order and c-axial relaxor behavior. The correlation among domain width, film thickness, and domain curvature suggested an ultralow domain wall energy in P(VDF-TrFE) near its morphotropic phase boundary, whereas the stabilization of local ferroelectric order from toroidal order was also manifested. A novel toroidal polar structure was finally presented, where a “toroidal polar micro-region” structure derived from the slush-like polar structure in relaxor P(VDF-TrFE).