Fluorination of Black Phosphorus—Will Black Phosphorus Burn Down in the Elemental Fluorine?

Abstract

Black phosphorus (BP) represents a promising tunable bandgap alternative to graphene and other 2D materials in the field of semiconductors. However, its reactivity toward covalent modification of its surface (as a key to its bandgap adjustment) is scarcely reported. Here a method of covalent modification of BP involving reaction with fluorine is reported. Other allotropes of phosphorus are known to react violently with fluorine resulting in its complete burning down and formation of gaseous phosphorus pentafluoride. The results of our fluorination experiments conducted in analogy to the procedures used for fluorination of graphene indicate a successful binding of fluorine to BP. This route of modification of BP opens new possible ways toward covalent modification of the surface of this promising material.

Self‐Healable Black Phosphorus Photodetectors

“…Three typical Raman peaks located at 360.9, 438.4, and 466.5 cm −1 can be donated to the A 1 g , B 2g , and A 2 g vibrational modes of P in BP QDs, and there are no peaks can be donated to PIL‐TFSI . Besides, it can be seen that there are only slight changes in the ratio of peak intensities and no additional peaks can be detected, indicating no significant changes in the crystallinity of the BP QDs after the encapsulation process, which is consistent with the previous literature …”

“…Nevertheless, the intensity located around 133.66 eV is slightly higher in the spectrum of BP‐PIL than that in pristine BP QDs, which can be explained by the overlap of PO and PF bonds (Figure e) . The fluorine is obviously visible in the XPS spectrum of the PIL‐TFSI encapsulated BP QDs as shown by the typical F 1s signal with the binding energy located at 688.29 eV (Figure d) which is consistent with the previous reports . Compare to the F 1s signals of PIL‐TFSI with the binding energy around 688.06 eV (Figure S2b, Supporting Information), there is an additional electronically signal of F 1s located around 695.01 eV that can be detected in the spectrum of BP‐PIL as shown in Figure f, which can be explained by the unintentional fluorination of BP QDs during the encapsulation process as well as the PF covalent bond created at the interface of BP QDs …”

“…47‐1624) according to the previous reports . It can be seen that the peaks only exhibit a little shift (≈0.2°) in the pattern of BP‐PIL compared to pristine BP QDs, which can be explained by the possible formation of PF bonds taking place at the edges of BP QDs during the encapsulation process . The observed little swell from 10° to 40° can be ascribed to the amorphous PIL‐TFSI.…”

Activating the electrode–electrolyte interface via a ZnO@black phosphorus modulation layer for dendrite-free Li metal anodes

“…36,37 The P 2p spectrum can be fitted with three peaks at 130.1, 130.9 and 134.5 eV, which can be assigned to P 2p 3/2 and P 2p 1/2 of BP, and P-O bonds, respectively. 34 All these results confirm the successful synthesis of ZnO@BP nanosheets.…”

Simulated Infrared and Raman Spectra of Phosphorus Allotropes

“…Moreover, in literature, the B 1g and B 3g (B 2g in our simulations) modes were observed in an investigation of the edge phonons of black phosphorus crystals as reported in Reference [61], as well as in the work of Plutnar et al in Reference [66].…”