Qiu Pengcheng, Wang Jiameng, Kojima Takahiro, Kazumi Kenji, Sato Hiroyasu, Komatsu Naoki, Fukami Kazuhiro, Sakaguchi Hiroshi
Institute of Advanced Energy, Kyoto University, Uji, Kyoto 611-0011, Japan.
Department of Materials Science and Engineering, Kyoto University, Kyoto, Kyoto 606-8501, Japan.
Angew Chem Int Ed Engl. 2025 Feb 3;64(6):e202421571. doi: 10.1002/anie.202421571. Epub 2025 Jan 7.
A tubular strand of phosphorus composed of vectorially aligned pentagons has been theoretically predicted as a new allotrope of phosphorus with a polar structure, expecting potential applications. However, it has not been successfully synthesized yet due to the difficulty of creating isolated strands to avoid interchain bonding. Here, such an allotrope named "orange phosphorus" was successfully produced using a photo-assisted synthesis from an amorphous film of solution-processable NaP precursors. A green laser irradiation initiated the phase transition of precursors, inducing chemical reactions like topochemical polymerization and rearrangement, creating a 1D chain of orange phosphorus. 3D electron diffraction crystallography showed that the molecular structure of orange phosphorus consists of one-dimensional polar pentagonal-tubes made up of [P8]P2[ repeat units. Orange phosphorus demonstrates excellent piezoresistivity due to its high strain-sensitive 1D chain structure, showing strain-induced Raman shifts. Its gauge factor exceeds those of 2D materials such as black phosphorus and transition metal dichalcogenides. These findings indicate that orange phosphorus has great potential for use in strain sensor applications.
理论上预测，由矢量排列的五边形组成的管状磷链是一种具有极性结构的新型磷同素异形体，有望得到潜在应用。然而，由于难以制备出孤立的链以避免链间键合，它尚未成功合成。在此，通过光辅助合成法，利用可溶液加工的NaP前驱体非晶膜成功制备出了这种名为“橙色磷”的同素异形体。绿色激光辐照引发前驱体的相变，诱导发生拓扑化学聚合和重排等化学反应，生成一维橙色磷链。三维电子衍射晶体学表明，橙色磷的分子结构由由[P8]P2[重复单元组成的一维极性五边形管构成。橙色磷因其高应变敏感的一维链结构而表现出优异的压阻特性，呈现出应变诱导的拉曼频移。其应变系数超过了二维材料如黑磷和过渡金属二硫属化物。这些发现表明橙色磷在应变传感器应用中具有巨大潜力。
