<br>砌块对称性对堆叠式二维聚酰亚胺共价有机框架能带结构的影响,ACS Omega

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砌块对称性对堆叠式二维聚酰亚胺共价有机框架能带结构的影响
ACS Omega ( IF 3.7 ) Pub Date : 2023-12-05 , DOI: 10.1021/acsomega.3c06496
Mateusz Wlazło ₁ , Keiichiro Maegawa _{1,

2} , Atsushi Nagai ₁

Affiliation

共价有机骨架 (COF) 是一类结晶多孔材料，完全由有机元素、碳、氧、氢以及通常的氮或硼构成。它们形成轻质、机械刚性和化学稳定的网络，具有许多优点，但它们的低溶解度和差的可加工性给开发大规模薄膜或膜带来了问题。二维 (2D) COF 具有周期性多孔结晶性、功能性、模块化和分层一维 (1D) 传输通道。所有这些特性，加上所选 COF 的半导体特性，使它们成为光电器件集成的有趣候选者。因此，从计算和结构上探索 COF 的半导体性并确定其最终潜力仍然是一个挑战。在此，我们使用密度泛函理论计算报告了聚酰亚胺-COF 材料可能的半导体特性和结果。我们的分析包括以苯六甲酸三酐（MTA）为主要结构结设计的苯六三酰亚胺框架的单层和多层（AA-和AB-堆叠模式），包括MTI-TAPB-COF，它之前是通过MTA和的缩合反应合成的1,3,5-三(4-氨基苯基)苯(TAPB)，以及其他先前未报道的基于MTA的结构。由于结构单元对称性（C ₃ + C ₂和C ₃ + C ₃ ）的差异以及通过苯或通过吡啶环的不同化学键，选择了各自的框架。我们发现聚酰亚胺多层膜很稳定并且具有不同的电子特性。每个结构（单层和堆叠）所表现出的有限带隙对原子排列很敏感。堆叠将色散引入到材料的平带结构中，该结构似乎对堆叠方向高度敏感。每个 COF 的堆叠效果相似，但能带结构变化的幅度不同，并且取决于构建块的对称性。

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Influence of Building Block Symmetry on the Band Structure of Stacked 2D Polyimide Covalent Organic Frameworks

Covalent organic frameworks (COFs) are a class of crystalline porous materials distinctively built solely from organic elements, carbon, oxygen, hydrogen, and often nitrogen or boron. They form light, mechanically rigid, and chemically stable networks that have many advantages, but their low solubility and poor processability create issues with developing large-scale films or membranes. Two-dimensional (2D) COFs possess periodic porous crystallinity, functionality, modularity, and layered one-dimensional (1D) transport channels. All of these traits, along with the semiconducting properties of selected COFs, make them interesting candidates for integration in optoelectronic devices. Therefore, it is still a challenge to explore computationally and structurally the semiconductivity of COFs and to determine their final potential. Herein, we report on the possible semiconducting properties and results of polyimide–COF materials using density functional theory calculations. Our analysis includes monolayers and multilayers (AA- and AB-stacked modes) of mellitic triimide frameworks designed from mellitic trianhydride (MTA) as the main building knot, including MTI-TAPB-COF, which was previously synthesized from the condensation reaction of MTA and 1,3,5-tris(4-aminophenyl)benzene (TAPB), and other previously unreported structures based on MTA. Respective frameworks have been selected due to the difference in building block symmetry (C₃ + C₂ and C₃ + C₃) and different chemical linkages, either by benzene or by pyridine rings. We find the polyimide multilayers to be stable and with varying electronic properties. The finite band gap exhibited by every structure (monolayer and stacked) was sensitive to atomic arrangement. Stacking introduces dispersion to an otherwise flat band structure of the materials, which appeared to be highly sensitive to stacking direction. The effect of stacking was similar for each COF, but the magnitude of band structure change was different and dependent on the symmetry of the building blocks.

更新日期：2023-12-05

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