Designing polymers that facilitate exciton dissociation and charge transport is critical for the production of highly efficient all‐polymer solar cells (all‐PSCs). Here, the development of a new class of high‐performance naphthalenediimide (NDI)‐based polymers with large dipole moment change (Δµ_ge) and delocalized lowest unoccupied molecular orbital (LUMO) as electron acceptors for all‐PSCs is reported. A series of NDI‐based copolymers incorporating electron‐withdrawing cyanovinylene groups into the backbone (PNDITCVT‐R) is designed and synthesized with 2‐hexyldecyl (R = HD) and 2‐octyldodecyl (R = OD) side chains. Density functional theory calculations reveal an enhancement in Δµ_ge and delocalization of the LUMO upon the incorporation of cyanovinylene groups. All‐PSCs fabricated from these new NDI‐based polymer acceptors exhibit outstanding power conversion efficiencies (7.4%) and high fill factors (65%), which is attributed to efficient exciton dissociation, well‐balanced charge transport, and suppressed monomolecular recombination. Morphological studies by grazing X‐ray scattering and resonant soft X‐ray scattering measurements show the blend films containing polymer donor and PNDITCVT‐R acceptors to exhibit favorable face‐on orientation and well‐mixed morphology with small domain spacing (30–40 nm).

中文翻译：

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具有高性能的全聚合物太阳能电池高效电荷产生的大偶极矩变化的含氰乙烯撑的聚合物受体设计

设计有助于激子解离和电荷传输的聚合物对于生产高效全聚合物太阳能电池（all-PSC）至关重要。在这里，一类新的高性能的萘二酰亚胺的（NDI）的发展为基础的聚合物具有大偶极矩的变化（Δ μ _GE）和作为用于所有的PSC报道电子受体离域最低未占分子轨道（LUMO）。设计并合成了一系列基于NDI的吸电子氰基亚乙烯基基团（PNDITCVT-R），该共聚物具有2-己基癸基（R = HD）和2-辛基十二烷基（R = OD）侧链。密度泛函理论计算揭示了Δµ _ge的增强氰基亚乙烯基的结合导致LUMO的离域化和离域化。由这些新的基于NDI的聚合物受体制成的全PSC具有出色的功率转换效率（7.4％）和高填充因子（65％），这归因于有效的激子离解，平衡的电荷传输和抑制的单分子重组。通过掠射X射线散射和共振软X射线散射测量进行的形态学研究表明，包含聚合物供体和PNDITCVT-R受体的共混膜表现出良好的面朝取向和良好混合的形态，且具有较小的畴间距（30-40 nm） 。