Synthesis, Exfoliation, and Transport Properties of Quasi-1D van der Waals Fibrous Red Phosphorus

Abstract

Quasi-one-dimensional (quasi-1D) fibrous red phosphorus (RP) has triggered growing interest recently for its unique properties and promising applications in energy storage, sensing, and heterogeneous catalysis. However, attempts to explore its anisotropy and transport properties have progressed slowly. In this work, we report the fabrication of large-size and pure bulk fibrous RP crystals using a chemical vapor transport reaction by modifying growth kinetics. For the first time, the weak layer number-dependent anisotropic electronic structure of fibrous RP is revealed based on theoretical calculations. The b-axis-aligned fibrous RP nanoribbons with a high aspect ratio exceeding 1000 are easily prepared by facile liquid exfoliation. Impressively, the field-effect transistor device built with fibrous RP nanoribbons exhibits p-type transport behavior and a high mobility reaching 236.7 cm 2 V −1 s −1 with an On/Off ratio approaching 1.6 × 10 3 , which are superior to those of other reported RP-based materials in general. The results demonstrate the great potential of fibrous RP as a promising channel material and lay a solid foundation to further study the intrinsic properties of quasi-1D van der Waals materials.

Solution phase synthesis of the less-known Form II crystalline red phosphorus

“…5a), where it exhibits a wider adsorption band from UV to NIR frequency regions than a-RP (Fig. 5b); from the Tauc plot, 49,50 the ( hνF ( R ∞ )) 1/2 – hν curves of Form II RP reveal its bandgap of 2.02 eV, which is broader than that of a-RP (1.78 eV), bulk fibrous red phosphorus (1.86–1.95 eV), 23 and bulk violet phosphorus (∼1.9 eV). 51 The quantum confinement effect could conceivably be neglected for both samples (Fig.…”

“…S12 †) show the characteristic red phosphorus peaks around 352 cm −1 and 462 cm −1 . 42 Due to the relatively low symmetry of the probable monoclinic crystal system, 14 assignment of diverse Raman peaks becomes difficult, 23,43,44 especially when the atomic positions of phosphorus are unknown yet.…”

“…16 Among all the preparation strategies for crystalline red phosphorus, high-temperature vapor phase methods still vastly dominate the field. 15,[17][18][19][20] The products synthesized through sealed ampoules are usually highly crystalline, 21 uniformly deposited 22,23 and closely brought into contact with substrates. 19 In contrast, solution phase methods benefit from controllable fabrication, uniform size of products, superior yield and safety.…”

Topochemical Synthesis of Copper Phosphide Nanoribbons for Flexible Optoelectronic Memristors

“…In this work, inspired by the natural quasi1D atomic struc ture of crystalline red phosphorus nanoribbons (cRP NRs), [39,40] copper phosphide (Cu 3 P) nanoribbons (Cu 3 P NRs) are synthe sized topochemically from cRP NRs. Owing to the large inter layer distance of cRP, cation intercalation and crystallization of the metal phosphide proceed easily in the mild solvothermal environment.…”

One-Dimensional Atomic Chains for Ultimate-Scaled Electronics

“…Without any chemical complexity introduced by the multicompositions, elemental materials are pure and intrinsically homogeneous, promising for denser device integration. It is promising that elemental ACs composed of tellurium (Te), − selenium (Se), sulfur (S), phosphorus, and carbon , were experimentally reported. As a kind of “DNA-like” spiral ACs from group 16, hexagonal-packed Te and Se ACs demonstrated good environmental stability and high hole mobility, whereas the 1D S ACs showed conducting behavior .…”