Liu Zhifang, Sun Yilin, Cao Huaqiang, Xie Dan, Li Wei, Wang Jiaou, Cheetham Anthony K
Department of Chemistry, Tsinghua University, Beijing, 100084, China.
Institute of Microelectronics, Beijing National Research Center for Information Science and Technology (BNRist), Tsinghua University, Beijing, 100084, China.
Nat Commun. 2020 Aug 6;11(1):3917. doi: 10.1038/s41467-020-17622-6.
Phosphorene, monolayer or few-layer black phosphorus, exhibits fascinating anisotropic properties and shows interesting semiconducting behavior. The synthesis of phosphorene nanosheets is still a hot topic, including the shaping of its two-dimensional structure into nanoribbons or nanobelts. Here we report electrochemical unzipping of single crystalline black phosphorus into zigzag-phosphorene nanobelts, as well as nanosheets and quantum dots, via an oxygen-driven mechanism. The experimental results agree well with our theoretical calculations. The calculation for the unzipping mechanism study suggests that interstitial oxygen-pairs are the critical intermediate species for generating zigzag-phosphorene nanobelts. Although phosphorene oxidation has been reported, lengthwise cutting is hitherto unreported. Our discovery of phosphorene cut upon oxidation represents a previously unknown mechanism for the formation of various dimensions of phosphorene nanostructures, especially zigzag-phosphorene nanobelts. It opens up a way for studying the quantum effects and electronic properties of zigzag-phosphorene nanobelts.
磷烯,即单层或几层黑磷,具有迷人的各向异性特性,并呈现出有趣的半导体行为。磷烯纳米片的合成仍是一个热门话题,包括将其二维结构塑造为纳米带或纳米条带。在此,我们报告了通过氧驱动机制将单晶黑磷电化学解理为锯齿形磷烯纳米带,以及纳米片和量子点。实验结果与我们的理论计算吻合良好。解理机制研究的计算表明,间隙氧对是生成锯齿形磷烯纳米带的关键中间物种。尽管已有磷烯氧化的报道,但纵向切割迄今尚未见报道。我们发现磷烯在氧化时会被切割,这代表了一种此前未知的形成各种尺寸磷烯纳米结构,尤其是锯齿形磷烯纳米带的机制。它为研究锯齿形磷烯纳米带的量子效应和电子特性开辟了一条途径。