Abstract
Black phosphorus, an emerging layered material, exhibits promising applications in diverse fields, ranging from electronics to optics. However, controlled synthesis of black phosphorus, particularly its few-layered counterparts, is still challenging, which should be due to the unclear growth mechanism of black phosphorus. Here, taking the most commonly used Sn-I assisted synthesis of black phosphorus as an example, we propose a growth mechanism of black phosphorus crystals by monitoring the reactions and analyzing the as-synthesized products. In the proposed mechanism, Sn24P19.3I8 is the active site for the growth of black phosphorus, and the black phosphorus crystals are formed with the assistance of SnI2, following a polymerization-like process. In addition, we suggest that all Sn-I assisted synthesis of black phosphorus should share the same reaction mechanism despite the differences among Sn-I containing additives. Our results shown here should shed light on the controlled synthesis of black phosphorus and facilitate further applications of black phosphorus.
Highlights
With the rapid development of two-dimensional materials, orthorhombic black phosphorus (BP), assembled by puckered phosphorus layers of interlinked six-membered rings via van der Waals interactions, recently has attracted much research enthusiasm due to its layer-number-dependent properties (Hirsch and Hauke, 2018; Liu H. et al, 2018; Liu Y. et al, 2018)
Further powder X-ray diffraction (XRD) analysis shows that the as-synthesized Black Phosphorus (BP) crystals give three main diffraction peaks at ∼16, 34, and 52◦ (Figure 1D)
The XRD pattern reveals that the BP crystals are in orthorhombic phase with excellent crystallinity, while the three diffraction peaks indicate that the crystals grow in a highly oriented manner
Summary
With the rapid development of two-dimensional materials, orthorhombic black phosphorus (BP), assembled by puckered phosphorus layers of interlinked six-membered rings via van der Waals interactions, recently has attracted much research enthusiasm due to its layer-number-dependent properties (Hirsch and Hauke, 2018; Liu H. et al, 2018; Liu Y. et al, 2018). The Sn and I containing mineralizers first decompose, forming SnI2 and Sn, and the decomposed compounds react with phosphorus vapor at elevated temperature to form Sn24P19.3I8.
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