Unencapsulated, exfoliated black phosphorus (BP) flakes are found to chemically degrade upon exposure to ambient conditions. Atomic force microscopy, electrostatic force microscopy, transmission electron microscopy, X-ray photoelectron spectroscopy, and Fourier transform infrared spectroscopy are employed to characterize the structure and chemistry of the degradation process, suggesting that O2 saturated H2O irreversibly reacts with BP to form oxidized phosphorus species. This interpretation is further supported by the observation that BP degradation occurs more rapidly on hydrophobic octadecyltrichlorosilane self-assembled monolayers and on H-Si(111) versus hydrophilic SiO2. For unencapsulated BP field-effect transistors, the ambient degradation causes large increases in threshold voltage after 6 h in ambient, followed by a ∼103 decrease in FET current on/off ratio and mobility after 48 h. Atomic layer deposited AlOx overlayers effectively suppress ambient degradation, allowing encapsulated BP FETs to ma...

Effective Passivation of Exfoliated Black Phosphorus Transistors against Ambient Degradation

Sodium-ion batteries have recently attracted significant attention as an alternative to lithium-ion batteries because sodium sources do not present the geopolitical issues that lithium sources might. Although recent reports on cathode materials for sodium-ion batteries have demonstrated performances comparable to their lithium-ion counterparts, the major scientific challenge for a competitive sodium-ion battery technology is to develop viable anode materials. Here we show that a hybrid material made out of a few phosphorene layers sandwiched between graphene layers shows a specific capacity of 2,440 mA h g−1 (calculated using the mass of phosphorus only) at a current density of 0.05 A g−1 and an 83% capacity retention after 100 cycles while operating between 0 and 1.5 V. Using in situ transmission electron microscopy and ex situ X-ray diffraction techniques, we explain the large capacity of our anode through a dual mechanism of intercalation of sodium ions along the x axis of the phosphorene layers followed by the formation of a Na3P alloy. The presence of graphene layers in the hybrid material works as a mechanical backbone and an electrical highway, ensuring that a suitable elastic buffer space accommodates the anisotropic expansion of phosphorene layers along the y and z axial directions for stable cycling operation. The sodiation–desodiation properties of few-layer phosphorene are mostly preserved by sandwiching the material between graphene layers, a behaviour that makes phosphorene–graphene hybrids a potentially suitable anode material for sodium-ion batteries.

A phosphorene–graphene hybrid material as a high-capacity anode for sodium-ion batteries

Phosphorus is one of the most abundant elements preserved in earth, and it comprises a fraction of ∼0.1% of the earth crust. In general, phosphorus has several allotropes, and the two most commonly seen allotropes, i.e. white and red phosphorus, are widely used in explosives and safety matches. In addition, black phosphorus, though rarely mentioned, is a layered semiconductor and has great potential in optical and electronic applications. Remarkably, this layered material can be reduced to one single atomic layer in the vertical direction owing to the van der Waals structure, and is known as phosphorene, in which the physical properties can be tremendously different from its bulk counterpart. In this review article, we trace back to the research history on black phosphorus of over 100 years from the synthesis to material properties, and extend the topic from black phosphorus to phosphorene. The physical and transport properties are highlighted for further applications in electronic and optoelectronics devices.

Semiconducting black phosphorus: synthesis, transport properties and electronic applications

One hundred years after its first successful synthesis in the bulk form in 1914, black phosphorus (black P) was recently rediscovered from the perspective of a 2D layered material, attracting tremendous interest from condensed matter physicists, chemists, semiconductor device engineers, and material scientists. Similar to graphite and transition metal dichalcogenides (TMDs), black P has a layered structure but with a unique puckered single-layer geometry. Because the direct electronic band gap of thin film black P can be varied from 0.3 eV to around 2 eV, depending on its film thickness, and because of its high carrier mobility and anisotropic in-plane properties, black P is promising for novel applications in nanoelectronics and nanophotonics different from graphene and TMDs. Black P as a nanomaterial has already attracted much attention from researchers within the past year. Here, we offer our opinions on this emerging material with the goal of motivating and inspiring fellow researchers in the 2D materials community and the broad readership of PNAS to discuss and contribute to this exciting new field. We also give our perspectives on future 2D and thin film black P research directions, aiming to assist researchers coming from a variety of disciplines who are desirous of working in this exciting research field.

https://www.pnas.org/content/pnas/112/15/4523.full.pdf

The renaissance of black phosphorus

The degradation of exfoliated black phosphorus in ambient conditions may limit its use in electronic devices. The combined effects of light irradiation and exposure to oxygen on mono- and multilayers of this material are now investigated.

Photooxidation and quantum confinement effects in exfoliated black phosphorus

There have been continuous efforts to seek novel functional two-dimensional semiconductors with high performance for future applications in nanoelectronics and optoelectronics. In this work, we introduce a successful experimental approach to fabricate monolayer phosphorene by mechanical cleavage and a subsequent Ar+ plasma thinning process. The thickness of phosphorene is unambiguously determined by optical contrast spectra combined with atomic force microscopy (AFM). Raman spectroscopy is used to characterize the pristine and plasma-treated samples. The Raman frequency of the A2g mode stiffens, and the intensity ratio of A2g to A1g modes shows a monotonic discrete increase with the decrease of phosphorene thickness down to a monolayer. All those phenomena can be used to identify the thickness of this novel two-dimensional semiconductor. This work on monolayer phosphorene fabrication and thickness determination will facilitate future research on phosphorene.

http://www.thenanoresearch.com/upload/justPDF/0446.pdf

Plasma-assisted fabrication of monolayer phosphorene and its Raman characterization

There have been continuous efforts to seek for novel functional two-dimensional semiconductors with high performance for future applications in nanoelectronics and optoelectronics. In this work, we introduce a successful experimental approach to fabricate monolayer phosphorene by mechanical cleavage and the following Ar+ plasma thinning process. The thickness of phosphorene is unambiguously determined by optical contrast combined with atomic force microscope (AFM). Raman spectroscopy is used to characterize the pristine and plasma-treated samples. The Raman frequency of A2g mode stiffens, and the intensity ratio of A2g to A1g modes shows monotonic discrete increase with the decrease of phosphorene thickness down to monolayer. All those phenomena can be used to identify the thickness of this novel two-dimensional semiconductor efficiently. This work for monolayer phosphorene fabrication and thickness determination will facilitates the research of phosphorene.

Xiangyang Ma

Papers

Plasma-assisted fabrication of monolayer phosphorene and its Raman characterization

Plasma-assisted fabrication of monolayer phosphorene and its Raman characterization