Wang Ning, Mao Nannan, Wang Zhien, Yang Xue, Zhou Xi, Liu Haining, Qiao Shanlin, Lei Xingfeng, Wang Junru, Xu Hua, Ling Xi, Zhang Qiuyu, Feng Qingliang, Kong Jing
College of Chemistry and Pharmaceutical Engineering, Hebei University of Science and Technology, Shijiazhuang, 050018, China.
Key Laboratory of Special Functional and Smart Polymer Materials of Ministry of Industry and Information Technology, School of Chemistry and Chemical Engineering, Northwestern Polytechnical University, Xi'an, 710072, China.
Adv Mater. 2021 Jan;33(1):e2005815. doi: 10.1002/adma.202005815. Epub 2020 Nov 27.
Due to strong interlayer interaction and ease of oxidation issues of black phosphorus (BP), the domain size of artificial synthesized few-layer black phosphorus (FL-BP) crystals is often below 10 µm, which extremely limits its further applications in large-area thin-film devices and integrated circuits. Herein, a hydrogen-free electrochemical delamination strategy through weak Lewis acid intercalation enabled exfoliation is developed to produce ultralarge FL-BP single-crystalline domains with high quality. The interaction between the weak Lewis acid tetra-n-butylammonium acetate (CH COOTBA) and P atoms promotes the average domain size of FL-BP crystal up to 77.6 ± 15.0 µm and the largest domain size is found to be as large as 119 µm. The presence of H and H O is found to sharply decrease the size of as-exfoliated FL-BP flakes. The electronic transport measurements show that the delaminated FL-BP crystals exhibit a high hole mobility of 76 cm V s and an on/off ratio of 10 at 298 K. A broadband photoresponse from 532 to 1850 nm with ultrahigh responsivity is achieved. This work provides a scalable, simple, and low-cost approach for large-area BP films that meet industrial requirements for nanodevices applications.
由于黑磷（BP）存在强烈的层间相互作用以及易氧化问题，人工合成的少层黑磷（FL-BP）晶体的畴尺寸通常小于10 µm，这极大地限制了其在大面积薄膜器件和集成电路中的进一步应用。在此，通过弱路易斯酸插层实现的无氢电化学剥离策略被开发出来，以制备高质量的超大FL-BP单晶畴。弱路易斯酸醋酸四丁基铵（CH₃COOTBA）与P原子之间的相互作用使FL-BP晶体的平均畴尺寸达到77.6±15.0 µm，并且发现最大畴尺寸高达119 µm。发现H⁺和H₂O的存在会急剧减小剥离后的FL-BP薄片的尺寸。电子输运测量表明，剥离后的FL-BP晶体在298 K时表现出76 cm² V⁻¹ s⁻¹的高空穴迁移率和10⁶的开/关比。实现了从532到1850 nm的具有超高响应率的宽带光响应。这项工作为满足纳米器件应用工业要求的大面积BP薄膜提供了一种可扩展、简单且低成本的方法。
